JP2003021929A - Dry developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-component developer that is removed by cleaning operation and recycled, ensures a very small reduction in the quantity of electric charges even when used after long-term storage and attains rapid buildup of electrostatic charge in use. SOLUTION: A toner image formed on an electrostatic latent image support is transferred one or more times onto a transfer member and the remaining toner is cleaned and returned to a developing section or a replenishment toner part through a recovering unit. An electric charge controlling agent comprises a metallic salicylate complex compound and its electric conductivity is <=950 μS/cm. When the quantity of electric charges on the toner matrix particles is represented by A, the quantity of electric charges on the toner after adding one or more additives to the toner matrix particles by B, the average particle diameter of the additives by C and the average particle diameter of the toner matrix particles by D, the value X calculated by the equation X=(B/A)×(ΣC/D) is in the range of -2.3<=X<=2.3. A bonding resin is an epoxy modified polyester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a developer and an image forming method used for developing an electrostatic latent image such as an electrophotographic method, an electrostatic recording method and an electrostatic printing method.

[0002]

2. Description of the Related Art Generally, in an electrophotographic apparatus, colored particles (a latent image of an electrostatic latent image bearing member is formed by adding external additives to base particles of at least a coloring agent, a binder resin and a charge control agent). Toner), the toner image is transferred to a transfer member, and then the toner image is fixed by a fixing device. After the toner transfer, the electrostatic latent image carrier is not transferred and the residual toner is cleaned by a cleaning device, collected in a recovery container, and discarded. If the image forming method using recycled toner that reuses the residual toner, resources can be effectively used.

However, when recycled toner is used, paper powder of transfer paper may be mixed in. Japanese Patent Laid-Open No. 7-20990
No. 2 discloses that, when a toner in which an external additive is buried or peeled off is used as a recycled toner, the amount of a releasing agent and the amount of an external additive are specified to suppress deterioration of a carrier and improve durability performance. Is listed. JP-A-11-95
Japanese Patent No. 553 describes that a combination of toners that maintains the relationship of reducing the external additive amount of the initial toner to be smaller than the external additive amount of the replenishing toner improves the fluidity and the charging stability of the developer. There is. Further, JP-A-11-153881 discloses that a toner having two types of fine particles and a toner having two types of fine particles added thereto has a toner charge amount in which the charge amount of a base material without addition of the additive and the additive are independent. It is described that the transfer efficiency is high and the waste toner is reduced by a combination between the charge amounts of In addition, JP-A-3-213
Japanese Patent No. 875 describes an example in which the conductivity of a resin is specified in such a material of colored particles (toner), and toner scattering, image fog, and transferability are good in a full-color toner. Further, as an example of adding an additive to the toner, JP-A-7-261446 describes that silica having a small particle size is added in order to improve the fluidity of the toner. Further, it is described that silica having a large particle size is added to prevent adhesion of toner. JP-A-10
No. 48928 discloses adding two kinds of additives, a hydrophobic inorganic compound and a hydrophilic inorganic compound having different specific surface areas and triboelectric charge amounts, to obtain an image free from toner scattering and fog, and in any environment. To obtain good high quality images. Japanese Patent Application Laid-Open No. 11-153881 describes that two kinds of additives, which are fine particles having a low charge amount and an irregular shape and fine particles having a high charge amount and a spherical shape, are added to maintain a stable transfer rate at a high level. Has been done. However, such a conventional toner, which has been removed by a cleaning operation and circulated and used, still does not exhibit completely sufficient characteristics, particularly sufficient charging characteristics when not stirred.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to remove a charge by a cleaning operation of a cleaning section and circulate it, and even if a developer before opening is used for a long period of time, a decrease in charge amount is extremely small. , Even if the charge amount has decreased, the charge amount quickly increases when used (opened),
Even after the copier is left unused for a long period of time, the amount of charge rises quickly during use,
No toner scattering and no background stain on non-image area 2
To provide a component developer.

[0005]

Means for Solving the Problems The above-mentioned problems are solved in (1) of the present invention, in which a developing portion for developing an electrostatic latent image on an electrostatic latent image bearing member is formed. , A two-component developer consisting of a carrier and toner is stored, the developer is circulated and conveyed on the developer carrier, and an electrostatic latent image is formed in a developing area in a gap between the developer and the opposing electrostatic latent image carrier. The image is developed, the toner image formed on the electrostatic latent image carrier is transferred onto the transfer member once or a plurality of times, and the electrostatic latent image carrier is cleaned by the cleaning unit. The toner cleaned in step 1 is returned to the developing section or the replenishing toner section through the toner collecting device, after which the latent image carrier prepares for the formation of the next electrostatic latent image, and the toner image is transferred to the final transfer member. The image forming method that is fixed by the fixing unit after being transferred A developer that can be used, wherein the toner particles include at least a colorant, a binder resin, and mother particles including a charge control agent to which an external additive is added, the charge control agent including a salicylic acid metal complex compound, The conductivity is 950 μS / cm or less, the charge amount of the toner base particles is A, the toner charge amount after adding at least one or more external additives to the toner base particles is B, and the average particle size of the external additives is C,
When the average particle diameter of the toner base particles is D, the following formula

The value of X obtained by substituting each value into X = (B / A) × (ΣC / D) is −2.3 ≦
X ≦ 2.3, the binder resin is an epoxy resin, an alkylene oxide adduct of a dihydric phenol or its glycidyl ether, a dihydric phenol,
A polyol (A) obtained by reacting an active hydrogen which reacts with an epoxy group with a compound having one in the molecule, an epoxy resin, a divalent phenol, and a compound having one active hydrogen in the molecule which reacts with an epoxy group. And a polyol (B) formed by reacting with

Further, the above-mentioned problem is (2) of the present invention, "the binder resin of the toner is at least two kinds of bisphenol A type epoxy resins in which the epoxy resins constituting the polyol (A) have different number average molecular weights. And the number average molecular weight of the low molecular weight component is 360 to 2000, and the number average molecular weight of the high molecular weight component is 3000 to 10000 ", and the two-component developer according to item (1)",
(3) "The toner binder resin is at least two bisphenol A type epoxy resins having different number average molecular weights as the epoxy resin constituting the polyol (A), and the low molecular weight component is 20 to 60 wt% and high. 5-4 molecular weight components
0 wt% is the two-component developer according to item (1) above, (4) "the binder resin of the toner,
The alkylene oxide adduct of a dihydric phenol or its glycidyl ether constituting the polyol (A) is a diglycidyl ether of an alkylene oxide adduct of bisphenol A, and the following general formula (1)

[0007]

[Chemical 2] n and m are the numbers of repeating units, each of which is 1 or more, and n + m = 2 to 8)), the two-component developer according to the above item (1) ", ( 5)
"The toner binder resin is an alkylene oxide adduct of a dihydric phenol constituting the polyol (A) or its glycidyl ether is 10 to 10% of the epoxy resin.
The first (1), characterized in that the content is 50 wt%
Two-component developer according to item, (6) "The toner binder resin has a number average molecular weight of the polyol (B) of 200 to 10".
And the toner binder resin contains 20 to 50 wt% of the polyol (B). The two-component developer according to item (1) above, "(8)
“Two-component developer according to item (1), wherein the toner binder resin is a polyester resin”,
(9) "Two-component developer according to any one of items (1) to (8), wherein the colorants of the toner are yellow, magenta, cyan and black which are different from each other". 10) “The surface of the carrier particles is coated with a resin, wherein the above (1) to (9)
The two-component developer according to any one of the items 1 to 4 ".

Further, the above-mentioned problem is (11) of the present invention, in which a carrier and a toner are provided in a developing section for developing an electrostatic latent image on an electrostatic latent image carrier having a developer carrier layer formed thereon. Containing a two-component developer, the developer is circulated and conveyed on the developer carrier, and an electrostatic latent image is developed in a development area in a gap between the developer and the opposing electrostatic latent image carrier. The toner image formed on the electrostatic latent image carrier is transferred onto the transfer member once or plural times, and the electrostatic latent image carrier is cleaned by the cleaning unit and then cleaned by the cleaning unit. After the toner is returned to the developing section or the replenishment toner section through the toner collecting device, the latent image carrier prepares for the formation of the next electrostatic latent image, and the toner image is transferred to the final transfer member. An image forming method of fixing by a fixing unit, The toner particles are composed of base particles including at least a colorant, a binder resin, and a charge control agent, to which an external additive is added, the charge control agent is composed of a salicylic acid metal complex compound, and the conductivity thereof is 950 μS / cm or less. The charge amount of the toner base particles is A, and the toner charge amount after adding at least one or more external additives to the toner base particles is B,
The average particle size of the external additive is C, and the average particle size of the toner base particles is D
When,

The value of X obtained by substituting each value into X = (B / A) × (ΣC / D) is −2.3 ≦
X ≦ 2.3 in the image forming method ”, (12)“ Using the two-component developer according to any one of (1) to (10) above. A method of developing an electrostatic latent image, which comprises forming a thin toner layer through a toner layer regulating member on a toner conveying member and then supplying the toner onto a latent image carrier to develop the latent image carrier. And (13) "the toner is a magnetic toner containing a magnetic material, and the image forming method according to the item (12)".

The present invention relates to a toner used in an image forming method for recycling the toner cleaned in a cleaning section, wherein an external additive is added to the base particles containing at least a colorant, a binder resin and a charge control agent. It consists of Among them, the charge control agent defines the conductivity of the salicylic acid metal complex compound. This conductivity is 950 μS / cm or less, and more preferably 800 μS / cm or less. By doing so, the toner is not scattered in the copying machine and the non-image area is not stained. If it is a two-component developer, the developer before opening (developer not used)
Even after using for a long period of time, the amount of charge is extremely low, and even if the amount of charge is low, the amount of charge quickly increases upon use (opening). Even when the copying machine is left unused for a long period such as summer vacation, the amount of charge rises quickly during use, so that toner is not scattered and scumming on non-image areas does not occur. By thus regulating the electric conductivity of the charge control agent, good charge application to the toner can be maintained. In addition, since the charge is appropriately attenuated, the above-described phenomenon of the problem is eliminated.

Further, the above object can be achieved by defining the charge amount before and after adding the external additive to the base particles.
The toner charge amount of the toner base particles of the present invention is A, the toner charge amount after adding at least one or more external additives to the toner base particles is B, the average particle size of the external additive is C, and the average particle size of the toner base particles. When the diameter is D, the following formula

The value of X obtained by substituting each value into X = (B / A) × (ΣC / D) is −2.3 ≦ X
It is achieved by an image forming toner characterized by being in the range of ≦ 2.3.

It is common practice to add an external additive to the toner base. The purpose is to improve the fluidity and appropriately polish the surface of the carrier or the surface of the latent image carrier to prevent deterioration of the carrier or the latent image carrier. Further, the purpose is to improve the charging property. The external additive added to the toner base particles is added to the toner base particles by agitation in the developing device, mechanical stress in the cleaning device, or in a recovery path recovered from the cleaning device to the developing device. The external additive may come off or be embedded (embedded) in the toner base particles. When such a result occurs, in particular, the charging property of the toner particles becomes unstable, so that, for example, the image density in the copy quality becomes low, or the image density becomes too high, and scumming occurs. Also, the toner may become significantly scattered inside the machine,
Further, the toner transfer efficiency is lowered, and it takes too much load to clean the latent image carrier in the cleaning step.
The toner may not be cleaned sufficiently.
In addition, in a place where the use environment is different, the fluctuation of the charge amount may significantly change in each environment, which promotes the above-mentioned trouble.

When the external additive added to the toner base particles is released or embedded in the toner base particles, the cause of unstable charge amount is investigated. One of them is It was confirmed that when the ratio (B / A) of the charge amount (A) and the charge amount (B) after adding the external additive to the toner base particles is far apart, the charge amount becomes significantly unstable. If this ratio is around 1, the shape is almost A = B, and even if the phenomenon that the external additive added to the toner base particles is released or embedded in the toner base particles occurs, it is almost A.
= Since the charge amount is close to B, the change in the charge amount between the toner particle surface and the carrier particle is small. On the other hand, when this ratio is small or large, the difference in charge amount from the carrier particles is remarkably large (the charge amounts are very different).
Therefore, when a phenomenon occurs in which the external additive added to the toner base particles separates or is embedded in the toner base particles, the charge amount is dominated by the charge of the toner base particles and the carrier,
After all, the charge amount (A) of the toner base particles contributes. Therefore, the charge (amount) in the developer becomes unstable, and the above-mentioned problems occur. In addition, a plurality of external additives may be added in some cases. Therefore, different particles may aggregate to increase the particle size of the additive. Therefore, if the ratio (C / D) of the average particle size (C) of the external additive and the average particle size (D) of the toner matrix is too small, the external additive is embedded in the toner matrix when the toner matrix and the external additive are mixed. Cheap. Also, during use in the machine, by stirring in the developing section,
Even when the temperature rises, it is extremely likely to be buried, so the effect of adding an external additive is unlikely to appear.

On the other hand, if this ratio is too large, the external additive is unlikely to adhere to or adhere to the toner base when the toner base and the external additive are mixed, and the amount of free external additive in the developer increases, which causes charging. The latent image may become unstable, the latent image carrier may be damaged, or the latent image carrier may be filmed so that the latent image formation is significantly impaired.

Further, in the roller fixing, if the roller surface is damaged, or if a type in which a release agent (silicon oil) is applied, it adheres to the application member and the release agent cannot be supplied, and an offset occurs. Furthermore, since the external additive is remarkably easily detached even during use in the machine, the above-mentioned problems are likely to occur at the same time. Therefore, the present invention defines the electric conductivity of the charge control agent, and determines the ratio (B / A) of the charge amount (A) of the toner base particles and the charge amount (B) of the toner base particles to which the external additive is added, and the external addition. Sum of the average particle size of the agent (C),
The ratio of the average particle size of the toner base particles to (D) (C /
An image forming method capable of obtaining good image quality by defining two products of D) and D).

According to the present invention, the end of the epoxy resin is capped and the end of the epoxy resin is capped with a polyol (A) having a polyosyalkylene part in the main chain, and the polyol (B) having no polyoxyalkylene part is contained. By using the toner that used together, environmental stability, stable fixed image,
It prevents transfer of the toner image to the vinyl chloride sheet on the copy-fixed image surface when it is in close contact, and further improves pulverizability to achieve high productivity. Especially when used for color toner, color reproducibility, It is effective for stable gloss and preventing curling of copy-fixed images.

The epoxy resin used in the polyol (A) used in the present invention is preferably bisphenol A.
It is obtained by binding epichlorohydrin with bisphenol such as bisphenol F or bisphenol F. The epoxy resin is at least two kinds of bisphenol A type epoxy resins having different number average molecular weights in order to obtain stable fixing characteristics and gloss, and the low molecular weight component has a number average molecular weight of 360 to 2
And the number average molecular weight of the high molecular weight component is 3,000.
It is preferably from 1 to 10,000. 20-60 wt% of low molecular weight component, 5-40 wt% of high molecular weight component
% Is preferable. If the low molecular weight is too high, or if the molecular weight is lower than 360, the gloss will be too high.
Further, the toner storability is not good. Further, when the amount of the high molecular weight component is too large, or when the molecular weight is higher than 10,000, the gloss is hard to appear. Further, the toner fixability is not good.

As the compound used in the present invention, the following are exemplified as the alkylene oxide adduct of dihydric phenol. Examples thereof include reaction products of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. In particular, glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

[0018]

[Chemical 3] n and m are the number of repeating units, each is 1 or more, and n + m = 2 to 8, preferably 2 to 6. )

The alkylene oxide adduct of dihydric phenol or its glycidyl ether is 10 to 50% by weight, preferably 10 to 40% by weight relative to the epoxy resin.
It is preferable that the content is wt%. If this amount is small, problems such as large curl of the copy paper occur, and if n + m is more than 8, and if it is too large, gloss is too much, and the toner storage stability is poor.

Examples of the monohydric phenols that react with the epoxy group used in the present invention include the following. Phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like can be mentioned. Furthermore, examples of the dihydric phenol used in the present invention include reaction products with bisphenols such as bisphenol A and bisphenol F. Various raw materials can be combined to obtain the polyol resin (A) of the present invention. The reaction is most preferable from the viewpoint of reaction stability.

The number average molecular weight of the polyol (B) used in the present invention is 200 to 10,000, and the polyol (B) is 10 to 50 wt%, preferably 20 to 50 wt.
% Is preferable. If the molecular weight is too small, the luster is too high, and the storage stability of the toner is not good. Also, the toner fixability is not good. Further, when the amount of the polyol (B) is small, the pulverizability is not good, and when it is too large, the curl of the copy paper becomes large, which causes problems.

The following method is used to measure the softening point of the polyol resin of the present invention. As a device for measuring the softening point, fully automatic dropping point device FP5 / FP manufactured by Metra
53 is used, and measurement is performed by the following procedure. The crushed sample is put in a melting pot and left for 20 minutes, then the sample is poured to the edge of the sample cup (droplet diameter 6.35 mm), cooled to room temperature, and set in a cartridge. F
P-5 control unit with temperature rising rate (1 ° C / mi
n) Set the measurement start temperature (set the initial softening temperature below 15 ° C.). The cartridge is attached to the FP-53 heating furnace, left for 30 seconds, and the start lever is pushed down to start the measurement. (The following measurement is done automatically.) Remove the cartridge when the measurement is completed.

The softening point (° C.) is calculated as follows. F
P-5 result display panel A value + correction value (adding the above correction value to the obtained result corresponds to the result of the Duran mercury method. The result display panel A value and the measurement start temperature (panel B , C value) is not more than 15 ° C., the test is repeated.) Next, as a device for measuring the glass transition point (Tg) by the DSC method in a nitrogen atmosphere, a Seiko Electronics DSC-200 is used. Then, measure according to the following procedure.
The sample is crushed, weighed 10 ± 1 mg in an aluminum sample container, and an aluminum lid is placed on the sample container. The glass transition point (Tg) is measured by the DSC method in a nitrogen atmosphere. The analysis conditions are as follows: the sample is heated from room temperature to 15 ° C at a heating rate of 20 ° C / min.
After heating to 0 ° C, leaving it at 150 ° C for 10 minutes, cooling the sample to 0 ° C at a temperature drop rate of 50 ° C / min, and leaving it for 10 minutes, and then again at 150 ° C in a nitrogen atmosphere (200 cc / min).
It is heated at a temperature rising rate of 20 ° C./min until DSC measurement. For Tg, the peak rising temperature is read using analysis software (Tg job).

The polyester resin used in the present invention is
It is preferable to use a polyester resin synthesized from a bisphenol type diol and a polycarboxylic acid. Examples of the bisphenol type diol include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy. Styrene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxybutylene (2) -2,2-
Bis (4-hydroxyphenyl) propane, polyoxypropylene (3) -bis (4-hydroxyphenyl) thioether, polyoxypropylene (2) -2,
2- (4-cyclohexanol) propane, polyoxyethylene (2) -2,6-dichloro-4-hydroxyphenyl, polyoxyethylene (2,5) -P, P-bisphenol, polyoxybutylene (4)- Bis (4-
Hydroxyphenyl) ketone, oxyethylene-2,
2-bis (4-hydroxyphenyl) propane, oxypropylene-2,2-bis (4-hydroxyphenyl) propane and the like. Other alcohol components may be ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, if necessary. Aliphatic polyols such as can be used.

Further, as the polyvalent carboxylic acid, for example,
Examples of the divalent aromatic carboxylic acid include derivatives such as phthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid and their esters. For example, as the trivalent aromatic polycarboxylic acid, 1,2,4- Benzenetricarboxylic acid,
1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and their anhydrides and esterified products Is mentioned.

Examples of the divalent aliphatic carboxylic acid include maleic acid, fumaric acid, succinic acid, adipic acid,
Sebacic acid, malonic acid, and divalent organic acid monomers obtained by substituting them with a saturated or unsaturated hydrocarbon group having 8 to 22 carbon atoms, their anhydrides, dimers of lower alkyl esters and linolenic acid, There are other divalent organic monomers and the like.

The acid value of the binder resin is 2 to 45. By thus defining the acid value, the adhesion between the recording medium (paper) and the toner is improved, and the toner fixability is improved. When the acid value is 2 or less, the familiarity between the cellulose fibers of the recording medium paper and the toner is not good, and the toner fixability is not good. In addition, since a toner having good chargeability and a good rising edge cannot be obtained, a background stain may occur on the image. On the other hand, when the acid value is 45 or more, the compatibility between the cellulose fiber of the paper and the toner becomes extremely good, and thus the fixability is good. However, since the charging property becomes strong, the charge amount becomes high and the image density becomes low especially in an environment of low temperature and low humidity. Further, if the toner density is increased in order to increase the image density, there is a problem that a lot of background stains occur. The acid value of the polyester resin of the present invention is JIS K
It measures according to the method of 0070.

In the toner of the present invention, other resins may be used together in order to improve fluidity, filming on a latent image carrier, pulverizability, storage stability, chargeability and the like. For example,
As examples, polystyrene, poly (p-chlorostyrene), homopolymers of styrene such as polyvinyltoluene, and substitution products thereof; styrene / p-chlorostyrene copolymers, styrene / propylene copolymers, styrene / vinyltoluene copolymers. , Styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / methyl methacrylate Copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / acrylonitrile copolymer, styrene / vinyl methyl ketone copolymer, Styrene / butadiene copolymer, styrene Isoprene copolymer, styrene /
Styrene-based copolymers such as maleic acid copolymers; acrylic acid ester-based homopolymers such as polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, and their copolymers; polyvinyl chloride , Polyvinyl derivatives such as polyvinyl acetate; polyester-based polymers, polyurethane-based polymers, polyamide-based polymers, polyimide-based polymers, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, etc. Alternatively, they can be used as a mixture, but are not particularly limited thereto. Among them, styrene-acrylic copolymer resin and polyester resin are more preferable in terms of good binding property, electric characteristics, cost and the like.

The following may be mentioned as specific examples of the colorant. Colorant for Black Carbon Black, Spirit Black, Aniline Black (CI PIGMENT BLACK 1)

Yellow colorant C. I. PIGMENT YELLOW 1 SYMLER FAST YELLOW GH-B (Dainippon Ink) C.I. I. PIGMENT YELLOW 3 SYMLER FAST YELLOW 10GH (Dainippon Ink) C.I. I. PIGMENT YELLOW 12 Linol Yellow GRO (Toyo Ink) SYMLER FAST YELLOW GF (Dainippon Ink) C.I. I. PIGMENT YELLOW 13 SYMLER FAST YELLOW GRF (Dainippon Ink) C.I. I. PIGMENT YELLOW 14 SYMLER FAST YELLOW 5GF (Dainippon Ink) C.I. I. PIGMENT YELLOW 17 SYMBLER FAST YELLOW 8GF (Dainippon Ink) Linol Yellow FGN (Toyo Ink) C.I. I. PIGMENT YELLOW 154 Chromofine Yellow 2080 (Dainichi Seika) C.I. I. PIGMENT YELLOW 180 PV Fast Yellow HG (Clariant)

Colorant for magenta C. I. PIGMENT RED 5 SYMLER FAST RED 4188N (Dainippon Ink) C.I. I. PIGMENT RED 22 Seikafast Scarlet G (Dainichiseika) SYMLER FAST SCALLET BG (Dainippon Ink) C.I. I. PIGMENT RED 48: 1 Linol Red 2B FG-3303-G (Toyo Ink), Sigmar Red 3109 (Dainippon Ink) C.I. I. PIGMENT RED 57: 1 Linol Red 6B FG-4215 (Toyo Ink) Symbrium Brilliant Carmine
6B273 (Dainippon Ink) PV Rubin L6B (Clariant) C.I. I. PIGMENT RED 112 Oriental Fast Red GR (Toyo Ink) C.I. I. PIGMENT RED 114 Pollux Pink PM-2B (Sumika Color) C.I. I. PIGMENT RED 122 Hostaperm Pink E 02 (Clariant) Fastogen Super Magenta R (Dainippon Ink) C.I. I. PIGMENT RED 166 Fastogen Super Red R (Dainippon Ink) C.I. I. PIGMENT RED 184 Permanent Rubin F6B (Clariant)

Cyan colorant C. I. PIGMENT BLUE 15: 3 Chromo fine Blue 4920 (Dainichi Seika) Fastogen Blue FGF (Dainippon Ink) Linol Blue FG-7351 (Toyo Ink) C.I. I. PIGMENT BLUE 16 Heliogen Blue 16 (BASF) C.I. I. PIGMENT GREEN 7 Phthalocyanine Green (Toyo Ink) C.I. I. PIGMENT GREEN 36 Cyanine Green 2 YL (Toyo Ink) The colorant amount is 0.1-5 with respect to 100 parts by weight of the binder resin.
0 parts by weight, more preferably 0.5 to 25 parts by weight is suitable.

Specific examples of the magnetic material include the following. Yellow YELLOW48 (made by Toda Kogyo Co., Ltd.), HY-100 (made by Titanium Kogyo Co., Ltd.), HY-200 (made by Titanium Kogyo Co., Ltd.), Y
-2, E-401 (manufactured by Toda Kogyo Co., Ltd.) Magenta 100ED, 120ED, 130ED, 140ED, 1
60ED, 180ED, 190ED, EC-101, E
C-131, EC-181 (all manufactured by Toda Kogyo Co., Ltd.) Cyan blue, EC-501 (manufactured by Toda Kogyo Co., Ltd.) Black KN-320, KH-340H, MS-350, HR-
340H, HR-370H, EC-301, EPT-1
000 (above, manufactured by Toda Kogyo Co., Ltd.), BL-SP, RB, B
L (manufactured by Titanium Industry Co., Ltd.)

In addition, as the magnetic fine powder, a material exhibiting magnetic sensitivity can be used regardless of the color. For example, metals such as iron, nickel, and cobalt, metal oxides, alloys, and the like. Materials often used include ferrosoferric oxide, ferric sesquioxide, oxides containing cobalt, ferrite, and nickel fine powder. The amount of magnetic material is 100 parts by weight of the binder resin,
The amount is preferably 1 to 30 parts by weight, more preferably 1.5 to 25 parts by weight.

As the charge control agent of the present invention, a salicylic acid metal complex compound such as a metal compound of an aromatic carboxylic acid, and
A metal complex compound of salicylic acid derivative is preferable. In particular, salicylic acid metal complex compounds such as aromatic carboxylic acid metal compounds and salicylic acid derivative metal complex compounds have a high charging speed and the charge distribution is uniform, so that stains on the electrostatic latent image bearing member and toner scattering into the machine occur. , Does not cause background stains on non-image areas. For example, the following formula is used.

[0036]

[Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a linear alkyl group or a branched unsaturated alkyl group. R ₁ and R ₂ , R ₂ and R 4 ₃ or R ₃ and R
₄ may form an aromatic ring which may have a substituent by a bond. m represents an integer of 3 or more, and n
Indicates an integer of 2 or more. M is Cr, Zn, Al, N
It represents a metal selected from i, Co, Fe, Ti, Mn, Si, and Sn. )

In the present invention, the amount of the charge control agent used is determined by the type of binder resin, the additive used, and the toner production method including the dispersion method, and is not uniquely limited. It is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 1 to 5 parts by weight is preferable.
If the amount is less than 0.1 parts by weight, the toner is insufficiently charged, which is not practical. When the amount is more than 10 parts by weight, the chargeability of the toner is too large, and in the case of using two components, the electrostatic attraction with the carrier increases, so that the flowability of the developer and the image density decrease.

The charge control agent may be used in combination with a plurality of charge control agents, if necessary. The procedure of the method for measuring the electric conductivity of the charge control agent is to put 5 g of the sample into a 300 ml beaker. 90 ml of ion-exchanged water and 10 ml of methyl alcohol are put into a 100 ml graduated cylinder. The above liquid is gradually added to the sample to wet it. Weigh this,
Boil for 5 minutes. After cooling in a cooling bath, ion-exchanged water is replenished to the original weight. Then, after stirring well, Toyo Filter Paper No. Filter with 2 and measure the electrical conductivity of the filtrate using an electrical conductivity meter.

The additive to the toner base particles is preferably 0.02 to 6.5 parts, more preferably 0.05 to 4.8 parts, based on 100 parts of the toner base. This additive has a specific surface area of 25-by nitrogen adsorption measured by the BET method.
Good action occurs in the range of 450 m ² / g.
Further, if necessary, it may be treated with a treating agent such as silicone oil, a coupling agent, an organic titanium compound or the like for the purpose of hydrophobization, charge control, etc., which is a preferable form.
For example, colloidal silica, hydrophobic silica, fatty acid metal salts (zinc stearate, aluminum stearate, etc.), metal oxides (titanium oxide, cerium oxide, silicon carbide, strontium titanate, aluminum oxide, tin oxide, antimony oxide, etc.) , Fluoropolymer, etc. may be contained.

Further, in order to use a so-called oilless fixing system in which a releasing agent such as oil is not used during toner fixing, waxes such as polyethylene wax, propylene wax and carnauba wax are contained in the toner particles. It can be realized by The amount of these used depends on the type of material used and the fixing method, but is preferably about 0.5 to 10.0% by weight and 1.0
It is more preferable to use about 8.0% by weight. As the method for producing the toner particles of the present invention, the above raw materials are
The toner base particles can be prepared by kneading by a known method such as a twin roll, a twin-screw extrusion kneader, a single-screw extrusion kneader, and the like, and performing known pulverization and classification such as mechanical or air flow type kneading. Further, a method of directly producing a toner from a monomer, a colorant and an additive by a suspension polymerization method or a non-aqueous dispersion polymerization method may be used.

The toner particle size is preferably 3 to 10 μm and 10 μm.
If it exceeds m, it is difficult to obtain smooth gradation and the resolution is also lowered. If it is less than 3 μm, the rise of the charge amount is good, but the toner scattering and the tendency to contaminate the carrier surface become remarkable. This toner particle size is measured by COULTER C
OWNER MODEL TA2 (manufactured by Coulter)
An interface (pores) of 100 μm is used by connecting an interface that outputs a number distribution and a volume distribution.

First, a toner measurement sample is dispersed in a surfactant added to an electrolytic aqueous solution. Another one of the above samples
% NaCl electrolyte, and a current is passed between both electrodes through the electrolyte in which electrodes are placed on both sides of the aperture of the aperture tube.
The particle size distribution of the particles is measured, and the volume average particle size is obtained from the volume average distribution. The toner particle size distribution is preferably 60% by number or less of toner having a particle size of 5 μm or less. If it is more than this, the toner is likely to adhere to the carrier, and the carrier in the developer is not efficiently charged with respect to the replenished toner.
The background portion of the image is likely to be stained. Furthermore,
The toners are easily aggregated, it is difficult to obtain a smooth image, and hollow characters occur in the character portion. 1
It is desirable that the toner particles having a particle diameter of 6 μm or more be 2% by volume or less. If it is more than this, the resolution is lowered and the image becomes rough. Further, the developed toner is less likely to be transferred to the transfer paper, and the character portion is apt to have a void. Further, at the time of kneading, a colorant or a dispersant for controlling the dispersed state of the magnetic material may be used together. Furthermore,
The toner base particles may be mixed and surface-modified by adding the above-mentioned additives and using a mixer or the like.

The carrier particles include inorganic / metal particles having an appropriate resistance, resin particles in which particles having a relatively low resistance are dispersed, and particles in which a core material having these as cores is provided with a coating layer. Can be used.

Examples of materials used for these are as follows. First, as an example of the inorganic / metal particles that can be used for the carrier particles, conventionally known particles can be used, for example, metals such as iron, cobalt, nickel, etc .;
Examples thereof include alloys and compounds such as magnetite, hematite and ferrite. The core material of such a coated carrier is generally produced by powder metallurgy. That is, 0.3 to 9
Weighing and mixing raw materials with fine primary particle size of micron
Grind after pre-sintering. Next, this is granulated into spherical particles of approximately 20 to 75 microns by a spray granulation process. Next, it sinters with a baking machine. During this sintering, the temperature is regulated so that the primary particles on the surface of the carrier retain their original shape (the primary particles do not become a continuous molten phase). Then, the particles are classified into arbitrary particles to obtain a carrier core material.

Next, as the resin particles of the carrier particles and / or the resin forming the coating layer, for example, polyethylene,
Polyolefin resin such as polypropylene, chlorinated polyethylene, chlorosulfonated polyethylene; polystyrene, acrylic (for example, polymethylmethacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether, polyviriketone, etc. Polyvinyl and polyvinylidene resins; vinyl chloride-vinyl acetate copolymers; silicone resins consisting of organosiloxane bonds or modified products thereof (eg modified products such as alkyd resins, polyester resins, epoxy resins, polyurethanes); polytetrafluoroethylene Fluorine resin such as polyvinyl chloride, polyvinylidene fluoride, polychlorotrifluoroethylene; polyamide; polyester; poly Urethane; polycarbonate;
Amino resin such as urea-formaldehyde resin, melamine-formaldehyde, melamine-formaldehyde-alcohol co-condensation; epoxy resin and the like. Among them, silicone resin or its modified product, fluorine resin, amino resin, especially silicone resin or its modified product is preferable as the material for the coating layer in view of preventing toner spent.

The silicone resin may be any conventionally known silicone resin, such as a straight silicone having only an organosiloxane bond represented by the following formula and a silicone modified with an alkyd, polyester, epoxy, urethane or the like. Resins may be mentioned.

[0047]

[Chemical 5] (Wherein R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ₂ and R ₃ are hydrogen groups, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group,
An alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a hydroxy group, a carboxyl group,
It is an ethylene oxide group, a glycidyl group or a group represented by the following formula.

[0048]

[Chemical 6] In the formula, R ₄ and R ₅ are a hydroxy group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and 2 carbon atoms.
Alkenyloxy group, phenyl group, phenoxy group, k, l, m, n, o, and p each represent an integer of 1 or more. )

Each of the above substituents has, in addition to an unsubstituted one, a substituent such as an amino group, a hydroxy group, a carboxyl group, a mercapto group, an alkyl group, a phenyl group, an ethylene oxide group, a glycidyl group, and a halogen atom. You may. The low resistance material used for controlling the volume resistivity of the resin particles and / or the carrier particles dispersed in the coating layer as described above may be a conventionally known material, examples of which include iron and gold. , A metal such as copper; an iron oxide such as ferrite and magnetite; a white conductive agent (titanium oxide-based, tin oxide-based, zinc oxide-based); a pigment such as carbon black. Among them, particularly by using a mixture of furnace black and acetylene black, which is one of carbon black, it is possible to effectively adjust the conductivity by adding a small amount of low resistance fine powder, and further to improve the resistance of resin particles / coating layer. Obtain carrier particles with excellent wear properties. The low resistance fine powder preferably has a particle diameter of about 0.01 to 10 μm, and is 1 to 100 parts by weight of the resin particles or the coating resin.
It is preferable to add 30 parts by weight, more preferably 2 to 2
0 parts by weight is preferred. Further, in the charge-imparting member resin particles and / or the coating layer, a silane coupling agent, a titanium coupling agent or the like is added for the purpose of improving the adhesiveness with the core particles or the dispersibility of the conductivity-imparting agent. You may add.

Examples of the silane coupling agent used in the present invention include compounds represented by the following general formula.

## STR00007 ## YRSiX _{3 wherein} X is a hydrolyzable group bonded to a silicon atom, and examples thereof include a chloro group, an alkoxy group, an acetoxy group, an alkylamino group and a propenoxy group. Y is an organic functional group that reacts with the organic matrix, and examples thereof include a vinyl group, a methacrylic group, an epoxy group, a glycidoxy group, an amino group, and a mercapto group. R is an alkyl group having 1 to 20 carbon atoms or an alkylene group.

Among these silane coupling agents, an aminosilane coupling agent having an amino group in Y is preferable in order to obtain a developer having a negative charging property, and an epoxy is used in Y to obtain a developer having a positive charging property. Epoxy silane coupling agents having groups are preferred. As a method for forming the coating layer, the coating liquid for forming the coating layer may be applied to the surface of the carrier core particles by a method such as a spraying method, a dipping method, a heating type kneader or a heating type Henschel mixer, as in the conventional method. The thickness of the coating layer is preferably 0.1 to 20 μm.

The present invention comprises carrier particles in which spherical particles are spherical particles and uneven portions are formed by a discontinuous phase whose surface state is melted. A resin coating layer is provided on the surface of the carrier particles, and uneven portions on the spherical particle surface after coating are provided. It has a coating layer that can be distinguished. Therefore, even if the surface of the core material is a convex portion, a coating layer is present so that the carrier resistance is appropriately maintained, the spent is suppressed, and a long-life (high durability) carrier is provided. That is, a uniform coating layer is provided along the circumferential shape of the core material, and the coating layer of the convex portion is thinner than that of the concave portion, while the coating layer of the concave portion is thicker. With such a configuration, due to the presence of the convex portion, the carrier resistance is appropriately suppressed from increasing, and due to the balance between the presence of the concave portion and the convex portion, the rising property of the charge with the toner is kept good, and Does not generate spent toner adhesion. If even a portion of the convex portion is exposed, toner adheres to the carrier in that portion, which leads to a decrease in the amount of charge and toner scattering. Also, if a coating layer is provided like a shell without conforming to the circumferential shape of the surface of the core material (the yolk is the core material in the image of an egg), the spent toner will not adhere and the coating layer will be thick, so the developing section There is no problem even if the coating layer is abraded to some extent by stirring. However, problems such as high carrier resistance, high charge amount, low image density, and edge effects that cause no problem in line copy, but thin in the center of the image in solid copy cause in color copy. It occurs remarkably. The present invention provides a carrier having a long life (high durability) by suppressing the increase in carrier resistance due to the presence of the protrusions and maintaining good chargeability with the toner by the balance of the presence of the recesses.

The resistance of carrier particles is 10 ⁸ to 10 ¹⁵ Ωc
m is good. When it is 10 ¹⁵ Ωcm or more, the edge effect is large and the graininess of the image is large. Further, although character copying is not a big problem, the above-mentioned problem is greatly highlighted when a picture is copied when it is a color copy. Furthermore, the ears of the carrier become hard during development, and streaks and unevenness are likely to occur. When it is 10 ⁸ Ωcm or less, carrier adhesion is likely to occur, the latent image carrier is easily scratched by the substance, and the latent image is liable to be disturbed, resulting in a marked deterioration of image quality.

The resistance is measured as follows. Area 10c under the environment of 20 ℃ / 60% RH
² m of ² m ² (4 cm long, 2.5 cm wide) electrode plates
After placing the sample to the extent that it overflows into the cells formed facing each other at an interval of m, tapping operation is performed in this state to drop the cells on the flat plate from the position of 15 mm in height.
The carrier sample is filled in the cell by repeating the process.
Next, excess carriers on the cell are removed, and then a DC electric field of 500 V / cm is applied to the electrode plate to obtain the resistance.

[0055]

EXAMPLES The present invention will now be described in more detail with reference to examples. <Synthesis Example of Polyol Resin> [Synthesis Example 1] 378.4 g of low molecular weight bisphenol A diglycidyl ether (number average molecular weight: about 360) was added to a stirring device, a thermometer, a nitrogen inlet, and a separal flask equipped with a cooling tube.
Polymer bisphenol A-type condensed diglycidyl ether (number average molecular weight: about 2700) 86.0 g, bisphenol A-type propylene oxide adduct diglycidyl compound (in the general formula (1), n + m: about 2.1) 1
91.0 g, bisphenol F274.5g, p-cumylphenol 70.1g, and xylene 200g were added.
Under nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of a modified epoxy polyol resin having a softening temperature of 109 ° C. and a Tg of 58 ° C. was obtained. (Hereinafter referred to as Resin 1)

[Synthesis Example 2] Using the apparatus of Synthesis Example 1,
Low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 360) 205.3 g, high molecular weight bisphenol A type condensation type diglycidyl ether (number average molecular weight:
About 3000) 54.0 g, a bisphenol A-type propylene oxide adduct diglycidyl compound (in the general formula (1), n + m: about 2.2) 432.0 g, bisphenol F282.7 g, p-cumylphenol 2
A separal flask was charged with 6.0 g and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 109 ° C and a Tg of 58 ° C. (Hereinafter referred to as resin 2)

[Synthesis Example 3] Using the apparatus of Synthesis Example 1,
252.6 g of low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 360), high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight:
Approximately 10,000) 112.0 g, bisphenol A-type propylene oxide adduct diglycidyl compound (in the general formula (1), n + m: approximately 5.9) 336.0 g,
255.3 g of bisphenol AD, 44.1 g of p-cumylphenol and 200 g of xylene were charged in a separal flask. In a nitrogen atmosphere, raise the temperature to 70 to 100 ° C,
Lithium chloride (0.183 g) was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours to give a softening temperature of 109 ° C. and Tg of 58 ° C.
1000 g of the modified epoxy polyol resin of was obtained. (Hereinafter referred to as resin 3)

[Synthesis Example 4] Using the apparatus of Synthesis Example 1,
Of low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 2400) 289.9 g, high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight: about 10000) 232.0 g, bisphenol A type ethylene oxide adduct Diglycidyl compound (n + m in the general formula (1): about 6.0) 309.0
g, bisphenol AD117.5 g, p-cumylphenol 51.6 g, and xylene 200 g were charged in a separal flask. Under nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. , Softening temperature 116 ° C, Tg6
1000 g of a modified epoxy polyol resin at 1 ° C. was obtained.
(Hereinafter referred to as resin 4)

[Synthesis Example 5] Using the apparatus of Synthesis Example 1,
Low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: 460) 430.0 g, high molecular weight bisphenol A type condensation type diglycidyl ether (number average molecular weight: about 6500) 188.0 g, bisphenol A type ethylene oxide adduct diglycidyl Compound (n + m in the general formula (1): about 5.9) 116.0 g, bisphenol F209.2 g, p-cumylphenol 4
A separal flask was charged with 7.5 g and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was performed for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 107 ° C and a Tg of 57 ° C. (Hereinafter referred to as resin 5)

[Synthesis Example 6] Using the apparatus of Synthesis Example 1,
244.5 g of low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 680), high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight:
Approximately 6500) 188.0 g, bisphenol A-type ethylene oxide adduct diglycidyl compound (n + m in the general formula (1): approximately 7.9) 348.0 g, bisphenol AD169.9 g, p-cumylphenol 49.6 g Then, 200 g of xylene was charged into a separal flask. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for ~ 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 112 ° C and a Tg of 59 ° C. (Hereinafter referred to as resin 6)

[Synthesis Example 7] Using the apparatus of Synthesis Example 1,
258.3 g of low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 680), high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight:
Approximately 6500) 199.0 g, bisphenol A-type ethylene oxide adduct diglycidyl compound (n + m in the general formula (1): approximately 4.2) 276.0 g, bisphenol A 198.3 g, p-cumylphenol 6
A separal flask was charged with 8.3 g and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 114 ° C. and a Tg of 60 ° C. (Hereinafter referred to as resin 7)

[Synthesis Example 8] Using the apparatus of Synthesis Example 1,
Low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 2000) 17.6 g High molecular weight bisphenol A type condensation type diglycidyl ether (number average molecular weight: about 11,000) 423.0 g, bisphenol A type ethylene oxide adduct diglycidyl Compound (n + m in the general formula (1): about 6.2) 385.0 g, bisphenol F109.6 g, p-cumylphenol 6
A separal flask was charged with 4.7 g and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 118 ° C and a Tg of 62 ° C. (Hereinafter referred to as resin 8)

[Synthesis Example 9] Using the apparatus of Synthesis Example 1,
Low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 300) 438.1 g, high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight:
Approximately 3000) 54.0 g, diglycidyl compound of bisphenol A-type ethylene oxide adduct (n + m in the general formula (1): approximately 1.9) 108.0 g, bisphenol AD347.9 g, p-cumylphenol 51.9 g Then, 200 g of xylene was charged into a separal flask. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for ~ 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 112 ° C and a Tg of 59 ° C. (Hereinafter referred to as resin 9)

[Synthesis Example 10] Using the apparatus of Synthesis Example 1, a low molecular weight bisphenol A type diglycidyl ether was prepared.
(Number average molecular weight: about 400) 251.2 g, high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight: about 6500) 50.0 g, bisphenol A type ethylene oxide adduct diglycidyl compound (the above-mentioned general formula (1 ), N + m: about 2.0) 400.0 g, bisphenol F276.0 g, p-cumylphenol 2
A separal flask was charged with 2.7 g and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 112 ° C and a Tg of 59 ° C. (Hereinafter referred to as resin 10)

[Synthesis Example 11] Using the apparatus of Synthesis Example 1, low molecular weight bisphenol A type diglycidyl ether
(Number average molecular weight: about 680) 82.3 g, high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight: about 6500) 683.0 g, bisphenol A type ethylene oxide adduct diglycidyl compound (the above-mentioned general formula (1 ), N + m: about 4.0) 125.0 g,
Bisphenol A 9.3 g, p-cumylphenol 18
A separal flask was charged with 0.0 g and 200 g of xylene. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was performed for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 118 ° C and a Tg of 63 ° C. (Hereinafter referred to as resin 11)

[Synthesis Example 12] 528.0 g of bisphenol A type diglycidyl ether (number average molecular weight: about 340), p-cumylphenol 472.0 g, and xylene 200 g were separated by using the apparatus of Synthesis Example 1. I put it in a flask. In a nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of an epoxy polyol resin having a molecular weight of about 350 was obtained. (Hereinafter referred to as resin 12)

[Synthesis Example 13] Using the apparatus of Synthesis Example 1, low molecular weight bisphenol A type diglycidyl ether
590.3 g (number average molecular weight: about 340), 263.9 g of p-cumylphenol, and 200 g of xylene were charged in a separal flask. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, and further 16
The temperature was raised to 0 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours to give a polymer having a molecular weight of about 1100.
1000 g of the epoxy polyol resin of was obtained. (Hereinafter referred to as resin 13)

[Synthesis Example 14] Using the apparatus of Synthesis Example 1, low molecular weight bisphenol A type diglycidyl ether
(Number average molecular weight: about 340) 627.3 g, bisphenol A 232.5 g, p-cumylphenol 140.2
g and xylene 200 g were charged in a separal flask.
In a nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of an epoxy polyol resin having a molecular weight of about 2000 was obtained. (Hereinafter referred to as resin 14)

[Synthesis Example 15] Using the apparatus of Synthesis Example 1, a low molecular weight bisphenol A type diglycidyl ether was prepared.
(Number average molecular weight: about 340) 647.6 g, bisphenol A 280.0 g, p-cumylphenol 72.4 g,
200 g of xylene was charged into a separal flask. Under nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of an epoxy polyol resin having a molecular weight of about 4000 was obtained. (Hereinafter referred to as resin 15)

[Synthesis Example 16] Using the apparatus of Synthesis Example 1, a low molecular weight bisphenol A diglycidyl ether was prepared.
(Number average molecular weight: about 340) 660.5 g, bisphenol A 310.0 g, p-cumylphenol 29.5 g,
200 g of xylene was charged into a separal flask. Under nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of an epoxy polyol resin having a molecular weight of about 10,000 was obtained. (Hereinafter referred to as resin 16)

[Synthesis Example 17] Using the apparatus of Synthesis Example 1, a low molecular weight bisphenol A type diglycidyl ether was prepared.
(Number average molecular weight: about 340) 661.9 g, bisphenol A313.4 g, p-cumylphenol 24.7 g,
200 g of xylene was charged into a separal flask. Under nitrogen atmosphere, the temperature was raised to 70 to 100 ° C., 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Then, 1000 g of an epoxy polyol resin having a molecular weight of about 12,000 was obtained. (Hereinafter referred to as resin 17)

[Synthesis Example 18] Using the apparatus of Synthesis Example 1, low molecular weight bisphenol A type diglycidyl ether
(Number average molecular weight: about 684) 411.9 g, diglycidyl compound of bisphenol A-type ethylenedioxide adduct (n + m in the general formula (1): about 3.8) 350.
0 g, bisphenol A 199.2 g, p-cumylphenol 180.0 g, and xylene 200 g were charged in a separal flask. A separal flask was charged with 313.4 g, p-cumylphenol 38.9 g, and xylene 200 g. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is distilled off under reduced pressure.
Polymerization was carried out for ~ 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 113 ° C and a Tg of 58 ° C. (Hereinafter referred to as resin 18)

<Production Example of Charge Control Agent> [Production Example 1] (Example of iron salicylate) 30 g of 3,5-di-tert-butylsalicylic acid and 7.2 g of sodium hydroxide were added to 30 ml of water, and the mixture was heated to 60 ° C. It was heated and dissolved. Also, ferric chloride (9.7 g) is added to water (3).
In addition to 00 ml, it was heated to 60 ° C. and dissolved. The 3,5-di-tert-butylsalicylic acid solution was added dropwise to the ferric chloride solution over 25 minutes. After the dropping was completed, the mixture was heated to 90 ° C. and reacted with stirring for 2 hours. Then, the precipitate is filtered and washed with water. At the time of washing with water, the number of times of washing was changed to obtain samples having different conductivity as shown in Table 1. Each sample was prepared by washing with water and drying at 115 ° C.

[0074]

[Table 1]

[Production Example 2] (Example of aluminum salicylate) An aqueous solution of 0.5 mol of sodium hydroxide and 3,5-di-t.
0.4 mol of ert-butylsalicylic acid was mixed and heated to dissolve. This solution contains 0.1 mol of Al ₂ (SO ₄ ) ₃
Is added to the aqueous solution of, and the mixture is heated and stirred, and then stirred and cooled to room temperature. Then, the precipitate is filtered and washed with water. This conductivity was 155 μs / cm.

[Production Example 3] (Example of chromium salicylate) An aqueous solution of 0.5 mol of sodium hydroxide and 3,5-di-t.
0.4 mol of ert-butylsalicylic acid was mixed and heated to dissolve. This solution contains 0.1 mol of Cr ₂ (SO ₄ ) ₃
Is added to the aqueous solution of, and the mixture is heated and stirred, and then stirred and cooled to room temperature. Then, the precipitate is filtered and washed with water. The conductivity was 210 μs / cm.

[Production Example 4] (Example of zinc salicylate) Aqueous solution of 0.5 mol of sodium hydroxide and 3,5-di-t
0.4 mol of ert-butylsalicylic acid is mixed and heated
Dissolved. This solution is 0.1 mol ZnCl ₂Water soluble
Add to the liquid, stir with heating, then stir to room temperature
Cooling. Then, the precipitate is filtered and washed with water. This conductivity
Was 95 μs / cm.

[Example 1] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle size of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained.

Binder resin: Resin of Resin 1 70 parts: Resin of Resin 15 30 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 4 1.5 parts Average for 100 parts by weight of the toner Particle size 0.015
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm. On the other hand, the carrier is a copolymer of 2-hydroxyethyl metallate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene, and a resin with a weight ratio of 75/25 is used as a ferrite core material having an average particle size of 50μ. 0.75% by weight
(Core material standard) was coated to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles after the addition of external additives.
The charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.024

In order to set and test the developer in the copying machine, the developer was prepared by mixing the toner with 2.5 parts of the toner in a ratio such that the total amount of the carrier was 100 parts. Then, the IMAGIO 420 (Ricoh copier) was modified so that the recycled toner could return to the toner supply section. When the developer was set and the initial image was formed, a good image was obtained. Further, when a continuous paper feed test of 100,000 sheets was carried out, a good image and no toner scattering were found in the copying machine, and when the copying process was stopped halfway and observed on the latent image carrier, the toner was found to be It was confirmed that there was no problem due to no stain due to.
After that, a test of 10,000 sheets of continuous paper feeding was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred. Further, when the produced developer was left to stand and an image was taken out, no particular problem occurred.

[Example 2] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 2 60 parts: Resin of resin 13 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 3] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 3 70 parts: Resin of resin 12 30 parts Toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 4] In Example 1, only the resin was changed as follows. Binder resin: Resin 4 of resin 60 parts: Resin 14 of resin 14 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 5] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 5 85 parts: Resin of resin 16 15 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 6] In Example 1, only the resin was changed as follows. Binder resin: Resin 6 resin 75 parts: Resin 17 resin 25 parts Toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 7] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 8 60 parts: Resin of resin 15 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 8] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 9 60 parts: Resin of resin 15 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 9] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 10 60 parts: Resin of resin 14 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 10] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 11 70 parts: Resin of resin 16 30 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 11] In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 2 45 parts: Resin of resin 13 55 parts Toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 12] In Example 1, only the resin was changed as follows. Binder resin: Resin 18 resin 60 parts: Resin 15 resin 40 parts A toner was prepared in the same manner as in Example 1, the same additives as in Example 1 were added, and the same carrier as in Example 1 was added. When used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

Example 13 In Example 1, only the resin was changed as follows. Binder resin: Resin of resin 1 60 parts: Resin of resin 13 30 parts: Resin of resin 16 10 parts A toner was prepared in the same manner as in Example 1, and the same additives as in Example 1 were added, When the same carrier as in Example 1 was used and tested in the same manner as in Example 1, the same result as in Example 1 was obtained.

[Comparative Example 1] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 3.6 μm. It was Binder resin: Styrene / acrylic resin 100 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1-1 0.2 parts Average particle size 0.29μ relative to 100 parts by weight of the toner
m of silica was mixed at a ratio of 0.7 part to prepare a negatively charging developing toner. On the other hand, the carrier is a copolymer of 2-hydroxyethyl metallate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene, and a resin having a weight ratio of 80/20 is used as a ferrite core material having an average particle size of 50μ. 0.75 wt% (based on the core material) was coated to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and carrier are charged in a pot, and mixing is performed at 150 rpm for 10 minutes, and then the developer is charged. Measure the quantity (Q / M). At this time, the toner is composed of toner base particles and toner particles after addition of external additives.
The charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after addition of external additive = −35 C: Silica having an average particle size of 0.29 μm D: Average particle size of 3.6 μm Toner base particles X = -2.8

In order to set and test the developer in the copying machine, a developer was prepared by mixing 2.5 parts of the toner and 100 parts of the carrier so that the total amount was 100 parts. Then, the IMAGIO 420 (Ricoh copier) was modified so that the recycled toner could return to the toner supply section. When the developer was set and the initial image was formed, the image density was low and the image was very uneven. In addition, when a 1000-sheet continuous paper feed test was performed, the image became more heavily soiled, and toner scattering occurred remarkably in the copying machine. Also, the copying process was stopped halfway and the latent image bearing member was observed. As a result, it was confirmed that the amount of dirt due to the toner and the amount of the additive were remarkably large. At this point, when the developer was observed with an electron microscope (SEM), many floating additives were confirmed. In addition, when the produced developer was left to stand and an image was taken out, there was a lot of background stain, and when the developer was observed, scattered toner was remarkable.

[Comparative Example 2] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 3.7 μm. It was Binder resin: Styrene / acrylic resin 100 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1-1 0.2 parts Average particle size 0.31 μ relative to 100 parts by weight of the toner
m of silica was mixed at a ratio of 0.7 part to prepare a positively chargeable developing toner.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene, and the weight ratio of the resin is 5/95.
A carrier of 0 μ was coated with a ferrite core material of 0.75 wt% (based on the core material). Next, prepare a pot made of stainless steel (diameter 60 mm, height 60 m
m, volume 50 cm ³ ) Weigh so that the total amount of the toner and carrier is 50 g. Toner density is 1.5%
Set (Toner = 0.75 g, Carrier = 49.25 g) to put toner and carrier into the pot,
After performing mixing at 150 rpm for 10 minutes, the charge amount (Q / M) of the developer is measured. At this time, the toner is composed of toner base particles and toner particles to which external additives have been added. Each toner is charged, and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Toner base particle Q / M = 1 B: Toner particle Q / M = 31 after adding an external additive C: Silica having an average particle size of 0.31 μm D: Average particle size 3.7 μm Toner base particle X = 2.6

In order to set and test the developer in the copying machine, the developer was prepared by mixing 2.5 parts of the toner and 100 parts of the carrier in a total amount. Then, the Spirit 2210 (Ricoh copying machine) was modified so that the recycled toner was returned to the toner supply section. When the developer was set and the initial image was formed, the image density was low and the image was very uneven.
Further, when a continuous paper passing test of 1,000 sheets was performed, the image was more contaminated with ground, and toner scattering occurred remarkably in the copying machine. Further, the copying process was stopped midway and the latent image bearing member was observed. However, it was confirmed that the amount of toner stains and the amount of additives were extremely large. At this point, when the developer was observed with an electron microscope (SEM), a large amount of the suspended additive was agitated. In addition, when the produced developer was left to stand and an image was taken out, there was a lot of background stain, and when the developer was observed, scattered toner was remarkable.

Comparative Example 3 A toner was prepared in the same manner as in Comparative Example 1 except that only the charge control agent in Production Example 1-1 was changed to that in Production Example 1-2. When the same test as in Example 1 was performed, the toner scattering was slightly smaller than that in Comparative example 1, but the result was similar to that in Comparative example 1.

[Comparative Example 4] A toner was prepared in the same manner as in Comparative Example 2 except that only the charge control agent in Production Example 1-1 was changed to that in Production Example 1-2. When the same test as in Example 2 was performed, the toner scattering was slightly less than in Comparative Example 2, but the result was similar to that in Comparative Example 2.

Example 14 A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle size of 4.5 μm. It was Binder resin: Resin of resin 2 70 parts: Resin of resin 13 30 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1-4 0.2 parts Average particle with respect to 100 parts by weight of the toner Diameter 0.3 μm
Silica was mixed at a ratio of 0.7 part to prepare a negatively chargeable developing toner.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene and a resin having a weight ratio of 75/25 and a ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and carrier are charged in a pot, and mixing is performed at 150 rpm for 10 minutes, and then the developer is charged. Measure the quantity (Q / M). At this time, the toner is composed of toner base particles and toner particles after addition of external additives.
The charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after addition of external additive = −35 C: Silica having an average particle diameter of 0.3 μm D: Average particle diameter of 4.5 μm Toner base particles X = -2.3

In order to set and test the developer in the copying machine, the developer was prepared by mixing the toner with 2.5 parts of the carrier in a ratio such that the total amount of the carrier was 100 parts. Then, the IMAGIO 420 (Ricoh copier) was modified so that the recycled toner could return to the toner supply section. When the developer was set and the initial image was formed, a good image was obtained. Furthermore, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found and toner scattering was not seen in the copying machine. Further, when the copying process was stopped midway and the latent image bearing member was observed, It was confirmed that there was no problem due to no stain due to.
After that, a test of 10,000 sheets of continuous paper feeding was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred.

[Example 15] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 4.5 µm. It was Binder resin: Resin of resin 2 70 parts: Resin of resin 13 30 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1-3 0.2 parts

To 100 parts by weight of the toner, 0.7 part by weight of silica having an average particle size of 0.3 μm was mixed to prepare a positively charging developing toner. On the other hand, the carrier is 2-
Copolymer of Hydroxyethyl Metal Relate / Methyl Methacrylate / Styrene and Vinylidene Fluoride /
The carrier was coated with a tetrafluoroethylene copolymer in a weight ratio of 5/95 and a ferrite core material having an average particle size of 50 μ and 0.75% by weight (based on the core material).

Next, a stainless pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and carrier are charged in a pot, and mixing is performed at 150 rpm for 10 minutes, and then the developer is charged. Measure the quantity (Q / M). At this time, the toner is composed of toner particles after addition of the toner base particle external additive. The toner is charged with each toner, and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M = 0 of toner base particles B: Q / M = 35 of toner particles after addition of an external additive C: Silica having an average particle size of 0.3 μm D: Toner base particles having an average particle size of 4.5 μm X = 2.3

In order to set and test the developer in the copying machine, the developer was prepared by mixing the toner with 2.5 parts of the toner in a ratio such that the total amount of the carrier was 100 parts. Then, the Spirit 2210 (Ricoh copying machine) was modified so that the recycled toner was returned to the toner supply section. When the developer was set and the initial image was formed, a good image was obtained. Further, when a continuous paper feed test of 100,000 sheets was carried out, a good image and no toner scattering were found in the copying machine, and when the copying process was stopped halfway and observed on the latent image carrier, the toner was found to be It was confirmed that there was no problem due to no stain due to. After that, a test of 10,000 sheets of continuous paper feeding was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred.

Example 16 A toner was prepared in the same manner as in Example 1 except that only the charge control agent in Example 4 was changed to that in Production Example 2. When tested, the same results as in Example 1 were obtained.

Example 17 A toner was prepared in the same manner as in Example 1 except that only the charge control agent in Example 4 was changed to that in Production Example 3. When tested, the same results as in Example 1 and Example 1 were obtained.

Example 18 A toner was prepared in the same manner as in Example 15 except that only the charge control agent in Example 15 was changed to that in Production Example 2-3. When the same test was performed, the same result as in Example 15 was obtained.

[Example 19] A toner was prepared in the same manner as in Example 15 except that only the charge control agent in Example 15 was replaced with that in Production Example 3. When the same test was performed, the same result as in Example 15 was obtained.

Example 20 A toner was prepared in the same manner as in Example 1 except that the charge control agent was changed from Production Example 4 to Production Example 1-2 in the toner formulation. When the same test as in Example 1 was performed, the same result as in Example 1 was obtained.

[Embodiment 21] In Embodiment 1, the charge control agent in the toner formulation is changed from Production Example 4 to Production Example 1-
A toner was prepared in the same manner as in Example 1 except that the toner of No. 3 was used, and the same test as in Example 1 was carried out. As a result, the same result as in Example 1 was obtained.

[Embodiment 22] Toner was prepared in the same manner as in Embodiment 15 except that the charge control agent used in Preparation Example 1-3 was changed from Preparation Example 1-2 to Preparation Example 1-2. Was prepared and tested in the same manner as in Example 15, and the same results as in Example 15 were obtained.

[Example 23] A toner was prepared in the same manner as in Example 15 except that the charge control agent in Example 15 was changed from those in Production Example 1-3 to those in Production Example 1-4. Was prepared and tested in the same manner as in Example 15, and the same results as in Example 15 were obtained.

Example 24 A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle size of 7.75 μm and a number% of 5 μ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Resin of resin 2 70 parts: Resin of resin 13 30 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 4 1.5 parts

For 100 parts by weight of the toner, 0.6 part of silica having an average particle diameter of 0.018 μm and an average particle diameter of 0.0
A mixture of 0.2 μm of 23 μm titanium was mixed in respective proportions to prepare a negatively charging developing toner. The carrier is the same as that used in Example 1, and a developer is prepared, and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particle = -17 B: Q / M of toner particle after addition of external additive = -19 C: (silica having average particle diameter 0.018 μm) + (average particle diameter 0.023 μm ) = 0.041 D: Average particle size 7.75 μm Toner base particles X = 0.0059 When tested in the same manner as in Example 1, the same result as in Example 1 was obtained.

Example 25 In Example 1, silica was treated with an organic silicon compound (TS-7).
No. 20, manufactured by Cabot Corporation) was tested in the same manner as in Example 1 and the same results as in Example 1 were obtained.

Example 26 A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle size of 7.75 μm. It was Binder resin: Resin of resin 2 70 parts: Resin of resin 13 30 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1-3 1.5 parts Wax: Paraffin wax 5.5 parts The toner 100 Average particle size 0.015 with respect to parts by weight
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm. On the other hand, the carrier used in Example 1 was tested in the same manner as in Example 1, and the same result as in Example 1 was obtained.

[Example 27] The toner used in Example 1 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle diameter of 50 μ, which is composed of a core material surface having irregularities. 230 ° C after coating
Then, the silicon film was cured under heating for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), surface irregularities could be observed even after clear coating. Further, it was confirmed by an electron beam microanalyzer that Si element was present also in the convex portion. When this carrier and toner were used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 28] The toner used in Example 1 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Then, the same core material as in Example 1 was coated. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Conductive agent: Ketjen Black ECDJ600 4 parts (manufactured by Lion Akzo) Toluene 1500 parts Tested in the same manner as in Example 1 using this carrier and toner. Similar results to Example 1 were obtained.

Example 29 The toner used in Example 1 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Then, the same core material as in Example 1 was coated. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Conductive agent: Ketjenblack ECDJ600 4 parts (Lion Akzo) Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Toluene 1500 parts This carrier and toner The same test as in Example 1 was carried out, and the same result as in Example 1 was obtained.

[Example 30] The toner used in Example 1 was used. On the other hand, the carrier was prepared by adjusting the coating liquid according to the following formulation and coating the core material. A synthetic example of an acrylic resin having a hydroxyl group is prepared by adding 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer and heating to 100 ° C., 400 g of styrene, 160 g of methyl methacrylate, 200 g of n-butyl acrylate.
g, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator were added dropwise over 5 hours.
Then, the contents were reacted for another 6 hours to obtain a resin having a solid content of 50%. (Hydroxyl value: 41 KOHmg / g, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) Fully substituted methylated benzoguanamine 2.6 parts (polymerization degree 1. 65, solid content 77%) Acrylic resin (the above synthetic product: solid content 50%) 10 parts Toluene 300 parts

A coating was prepared by mixing the methylated guanamine, an acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and toner were used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 31] The toner used in Example 1 was used. On the other hand, the carrier was prepared by adjusting the coating liquid according to the following formulation and coating the core material. A synthetic example of an acrylic resin having a hydroxyl group is prepared by adding 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer and heating to 100 ° C., 400 g of styrene, 160 g of methyl methacrylate, 200 g of n-butyl acrylate.
g, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator were added dropwise over 5 hours.
Then, the contents were reacted for another 6 hours to obtain a resin having a solid content of 50%. (Hydroxyl value: 41 KOHmg / g, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) Fully substituted methylated benzoguanamine 2.6 parts (polymerization degree 1. 65, solid content 77%) Acrylic resin (synthetic product: solid content 50%) 10 parts Conductive agent: Ketjen Black ECDJ600 2.5 parts (manufactured by Lion Akzo) Toluene 300 parts

A coating was prepared by mixing the above methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and toner were used and tested in the same manner as in Example 1, the same results as in Example 1 were obtained.

[Example 32] As a carrier, a coating solution was prepared according to the following formulation. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle diameter of 50 μ, which is composed of a core material surface having irregularities. 230 ° C after coating
Then, the silicon film was cured under heating for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), surface irregularities could be clearly observed even after coating. Further, it was confirmed by an electron beam microanalyzer that Si element was present also in the convex portion.

On the other hand, as the toner, a yellow toner was prepared as follows. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Yellow colorant: C.I. I. Pigment Yellow 180 5 parts Charge control agent: the product of Production Example 2 parts 2 parts This is pre-kneaded with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled, roughly crushed to 0.5 to 3 mm, and further crushed and classified to obtain an average particle size of 7.7.
A yellow toner having a number% of 5 μm or less and 5 μm or less of 12.85 and a volume% of 16 μm or more of 0.07 was obtained.

0.0 to 100 parts by weight of the toner
16 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.5 part to obtain a negatively chargeable toner. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = -18 B: Q / M of toner particles after addition of external additive = -23 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0026

A magenta toner was prepared by the following toner prescription. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Magenta colorant: C.I. I. Pigment Red 122 4 parts Charge control agent: of Production Example 4 2 parts This is premixed with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled, roughly crushed to 0.5 to 3 mm, and further crushed and classified to obtain an average particle size of 7.7.
A magenta toner having a number percent of 5 μ or less and 5 μ or less of 12.85 and a volume percent of 16 μ or more of 0.07 was obtained.

0.0 to 100 parts by weight of the toner
Silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) having a particle size of 16 μm was mixed at a ratio of 0.5 part to obtain a toner having a negative charging property. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = −14 B: Q / M of toner particles after addition of external additive = −19 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0028

Cyan toner was prepared by the following toner formulation. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Cyan colorant: C.I. I. Pigment Blue 15: 3 3 parts Charge control agent: the product of Production Example 2 2 parts This is premixed with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled, roughly crushed to 0.5 to 3 mm, and further crushed and classified to obtain an average particle size of 7.7.
A cyan toner having a number% of 5 μm or less and 5 μm or less of 12.85 and a volume% of 16 μm or more of 0.07 was obtained.

0.0 to 100 parts by weight of the toner
16 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.5 part to obtain a negatively chargeable toner. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = -18 B: Q / M of toner particles after addition of external additive = -22 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0025

A black toner was prepared by the following toner formulation. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Black colorant: Carbon black 8 parts Charge control agent: of production example 2 2 parts

This is pre-kneaded with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled and roughly crushed to 0.5 to 3 mm, and then further crushed and classified to have an average particle size of 7.75μ, and a number% of 5μ or less is 12.8.
A black toner having a volume% of 5,16 μ or more and 0.07 was obtained.

0.0 to 100 parts by weight of the toner
16 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.5 part to obtain a negatively chargeable toner. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = −13 B: Q / M of toner particles after addition of external additive = −18 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.00
29

The above carrier is used, and the total amount of 5 parts of the toner of each color and the carrier is 100.
By mixing in a ratio of parts, yellow, magenta, cyan, and black developers were prepared. For each color developer, the pre-tail 750 (a color copying machine manufactured by Ricoh Co., Ltd.) was modified so that the recycled toner was returned to the toner replenishing section. Then, when a developer was set and an image was output, the toner transferability was good, there was no toner dust in the image area, there was no toner loss in the character area, moderate image gloss was maintained, and there was no scumming.
A good image was obtained. Also, 10 ° C / 15%, 30 ° C
A good image was obtained even after printing 10,000 images in each environment of 90% / 90%.

[Example 33] In Example 32, only the binder resin was changed to the following. Other than that, Example 32
Yellow, magenta, cyan, and black toners were prepared in the same manner as described above, and the same tests as in Example 32 were performed using the carrier of Example 32, and the same results as in Example 32 were obtained. Binder resin: Resin 2 resin 60 parts: Resin 13 resin 40 parts

[Example 34] In Example 32, only the binder resin was changed to the following. Other than that, Example 32
Yellow, magenta, cyan, and black toners were prepared in the same manner as described above, and the same tests as in Example 32 were performed using the carrier of Example 32, and the same results as in Example 32 were obtained. Binder resin: Resin of resin 3 70 parts: Resin of resin 12 30 parts

[Example 35] In Example 32, only the binder resin was changed to the following. Other than that, Example 32
Yellow, magenta, cyan, and black toners were prepared in the same manner as described above, and the same tests as in Example 32 were performed using the carrier of Example 32, and the same results as in Example 32 were obtained. Binder resin: Resin 4 resin 60 parts: Resin 14 resin 40 parts

[Example 36] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 5 resin 85 parts: Resin 16 resin 15 parts

[Example 37] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 6 resin 75 parts: Resin 17 resin 25 parts

[Example 38] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following resin. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 8 resin 60 parts: Resin 15 resin 40 parts

[Example 39] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 9 resin 60 parts: Resin 14 resin 40 parts

[Example 40] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 10 resin 60 parts: Resin 14 resin 40 parts

[Example 41] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: 70 parts of resin 11: 30 parts of resin 16

[Example 42] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 2 resin 45 parts: Resin 13 resin 55 parts

[Example 43] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: 60 parts of resin 18: 40 parts of resin 15

[Example 44] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: 60 parts of resin 18: 40 parts of resin 15

[Example 45] Yellow, magenta, cyan and black toners were prepared in the same manner as in Example 32 except that only the binder resin was changed to the following. When the same test as in Example 32 was carried out using the carrier, the same result as in Example 32 was obtained. Binder resin: Resin 1 resin 60 parts: Resin 13 resin 30 parts: Resin 16 resin 10 parts

Example 46 In Example 32, the additives of the toner were changed as follows, the carrier of Example 32 was used, and the same test as in Example 32 was carried out. Similar results to 32 were obtained. Additive: 0.6 part of silica having an average particle diameter of 0.018 μm: 0.2 part of titanium having an average particle diameter of 0.023 μm X = 0.0059.

Example 47 In Example 32, silica was treated with an organic silicon compound (TS-
720, manufactured by Cabot Corp.) was tested in the same manner as in Example 32, and the same results as in Example 32 were obtained.

[Example 48] In Example 32, the toner used in Example 32 was used, and the carrier was 2-hydroxyethyl metal relate / methyl methacrylate /.
A styrene copolymer and a vinylidene fluoride / tetrafluoroethylene copolymer with a weight ratio of 75/25 are coated on a ferrite core material having an average particle diameter of 50 μ at 0.75% by weight (based on the core material). The carrier was coated. When this toner and the carrier were used and tested in the same manner as in Example 32, the same results as in Example 32 were obtained.

Example 49 In Example 32, the toner of Example 32 was used as the toner, and the coating liquid was prepared according to the following formulation as the carrier. And Example 32
The same core material was coated. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Toluene 1500 parts A test was conducted in the same manner as in Example 32 using this toner and carrier. Similar results to 32 were obtained.

Example 50 In Example 32, the toner of Example 32 was used as the toner, and the coating liquid was prepared as the carrier according to the following formulation. And Example 32
The same core material was coated. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Toluene 1500 parts A test was conducted in the same manner as in Example 32 using this toner and carrier. Similar results to 32 were obtained.

[Example 51] In Example 32, the toner used in Example 32 was used, and the carrier was prepared by adjusting the coating liquid according to the following formulation to coat the core material. A synthetic example of a hydroxyl group-containing acrylic resin was prepared by adding 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer, heating to 100 ° C., and adding 40 g of styrene.
A mixture of 0 g, 160 g of methyl methacrylate, 200 g of n-butyl acrylate, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator was added dropwise over 5 hours. Then react the contents for an additional 6 hours,
A resin having a solid content of 50% was obtained. (Hydroxyl number: 41 KOHmg
/ G, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) 2.6 parts of fully substituted methylated benzoguanamine (polymerization degree 1.65, solid content 77%) ) Acrylic resin (synthetic product: solid content 50%) 10 parts Toluene 300 parts

A coating was prepared by mixing the methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and toner were used and tested in the same manner as in Example 32, the same results as in Example 32 were obtained.

[Example 52] In Example 32, the toner of Example 32 was used, and the carrier was prepared by adjusting the coating liquid according to the following formulation and coating the core material. A synthetic example of a hydroxyl group-containing acrylic resin was prepared by adding 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer, heating to 100 ° C., and adding 40 g of styrene.
A mixture of 0 g, 160 g of methyl methacrylate, 200 g of n-butyl acrylate, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator was added dropwise over 5 hours. Then, the contents were reacted for another 6 hours to obtain a resin having a solid content of 50%. (Hydroxyl number: 41KOH
mg / g, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) 2.6 parts of fully substituted methylated benzoguanamine (polymerization degree 1.65, solid content 77) %) Acrylic resin (synthetic product: solid content 50%) 10 parts Conductive agent: Ketjen Black ECDJ600 2.5 parts (Lion Akzo) Toluene 300 parts

A coating was prepared by mixing the methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and toner were used and tested in the same manner as in Example 32, the same results as in Example 32 were obtained.

[Example 53] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle size of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained.

<Production Example of Polyester Resin 1> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, terephthalic acid and trimellitic acid were added, and the acid was obtained by condensation by a conventional method. Value 3.5 (K
OH mg / g) of resin was obtained. Binder resin: 100 parts of the production example of polyester resin 1 Colorant: Carbon black 11 parts Charge control agent: The production example 4 1.5 parts Average particle diameter 0.015 per 100 parts by weight of the toner
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene, and a resin having a weight ratio of 75/25 and a ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles to which external additives have been added. Each toner is charged and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.024

In order to set and test the developer in the copying machine, the developer was prepared by mixing 2.5 parts of the toner in a ratio such that the total amount with the carrier would be 100 parts. Then, the IMAGIO 420 (Ricoh copier) was modified to allow recycled toner to return to the toner supply section. When the developer was set and the initial image was formed, a good image was obtained. Further, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found, and toner scattering was not observed in the copying machine. Further, when the copying process was stopped halfway and observed on the latent image carrier, No stain due to toner was observed, and it was confirmed that there was no problem. After that, a test of 10,000 sheets of continuous paper passing was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred.

[Example 54] In Example 53, only the resin was changed as follows. <Production Example of Polyester Resin 2> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2
-Bis (4-hydroxyphenyl) propane, terephthalic acid and 1,2,4-benzenetricarboxylic acid were added and condensation was carried out by an ordinary method to give an acid value of 35 (KOHmg /
The resin of g) was obtained. Binder resin: Production example of polyester resin 2 100 parts Toner was prepared in the same manner as in Example 1, the same additives as in Example 53 were added, and the same carrier as in Example 54 was used. When tested in the same manner as in Example 53, the same results as in Example 53 were obtained.

[Example 55] In Example 53, only the resin was changed as follows. <Production Example of Polyester Resin 3> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and terephthalic acid were added and condensed by an ordinary method to give an acid value of 2.2 (KOHmg / The resin of g) was obtained. Binder resin: Production example of polyester resin 3 100 parts Toner was prepared in the same manner as in Example 53, and Example 53 was used.
When the same additive as in Example 53 was used and the same carrier as in Example 53 was used and the same test as in Example 53 was carried out, the same result as in Example 53 was obtained.

[Example 56] In Example 53, only the resin was changed as follows. <Production Example of Polyester Resin 4> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, terephthalic acid, succinic acid, trimellitic acid / is condensed by an ordinary method to give an acid value of 42. (KOHmg
/ G) of resin was obtained. Binder resin: Polyester resin 4 production example 100 parts Toner was prepared in the same manner as in Example 53, and Example 53 was used.
When the same additive as in Example 53 was used and the same carrier as in Example 53 was used and the same test as in Example 53 was carried out, the same result as in Example 53 was obtained.

[Example 57] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 4.5 µm. It was Binder resin: Polyester resin of Production Example 1 100 parts Colorant: Carbon black 11 parts Charge control agent: Production Example 3 0.2 parts Average particle diameter 0.3 μm with respect to 100 parts by weight of the toner
Silica was mixed at a ratio of 0.7 part to prepare a negatively chargeable developing toner.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene and a resin having a weight ratio of 75/25 and a ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and carrier are charged in a pot, and mixing is performed at 150 rpm for 10 minutes, and then the developer is charged. Measure the quantity (Q / M). At this time, the toner is composed of toner base particles and toner particles to which external additives have been added. Each toner is charged and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after addition of external additive = −35 C: Silica having an average particle diameter of 0.3 μm D: Average particle diameter of 4.5 μm Toner base particles X = -2.3

In order to set and test the developer in a copying machine, the developer was prepared by mixing 2.5 parts of the toner in a ratio such that the total amount with the carrier would be 100 parts. Then, the IMAGIO 420 (Ricoh copier) was modified so that the recycled toner could return to the toner supply section. When the developer was set and the initial image was formed, a good image was obtained. Furthermore, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found and toner scattering was not seen in the copying machine. Further, when the copying process was stopped midway and the latent image bearing member was observed, It was confirmed that there was no problem due to no stain due to.
After that, a test of 10,000 sheets of continuous paper passing was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred.

[Example 58] In Example 53, the charge control agent in the toner prescription was changed from Production Example 4 to Production Example 2
A toner was prepared in the same manner as in Example 53 except that the toner was replaced by the same toner, and the toner was tested in the same manner. The same results as in Example 53 were obtained.

[Example 59] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle size of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Polyester resin manufactured in Example 1 100 parts Colorant: Carbon black 11 parts Charge control agent: manufactured in Example 3 1.5 parts

To 100 parts by weight of the toner, 0.6 part of silica having an average particle diameter of 0.018 μm and an average particle diameter of 0.0
A mixture of 0.2 μm of 23 μm titanium was mixed in respective proportions to prepare a negatively charging developing toner. The carrier is that of Example 53, and a developer is prepared, and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particle = -17 B: Q / M of toner particle after addition of external additive = -19 C: (silica having average particle diameter 0.018 μm) + (average particle diameter 0.023 μm ) = 0.041 D: Average particle size 7.75 μm Toner base particles X = 0.0059 Next, the same test as in Example 53 was carried out.
Similar results were obtained.

[Example 60] A product obtained by treating silica in Example 53 with an organic silicon compound (TS-
720, manufactured by Cabot Corp.) was tested in the same manner as in Example 53, and the same results as in Example 53 were obtained.

Example 61 A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle size of 7.75 μm. It was Binder resin: from the production example of polyester resin 1 100 parts Colorant: carbon black 11 parts Charge control agent: from production example 1-2 1.5 parts Wax: paraffin wax 5.5 parts

Silica having an average particle size of 0.015 μm was mixed with 100 parts by weight of the toner at a ratio of 0.3 part to prepare a negatively chargeable developing toner. On the other hand, when the carrier used in Example 53 was used and tested in the same manner as in Example 53, the same results as in Example 53 were obtained.

[Example 62] The toner used in Example 53 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle diameter of 50 μ, which is composed of a core material surface having irregularities. 230 ° C after coating
Then, the silicon film was cured under heating for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), surface irregularities could be observed even after clear coating. Further, it was confirmed by an electron beam microanalyzer that Si element was present also in the convex portion. Using this carrier and toner, Example 53
When tested in the same manner as above, the same results as in Example 53 were obtained.

[Example 63] The toner used in Example 53 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Then, the same core material as in Example 53 was coated. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Conductive agent: Ketjen Black ECDJ600 4 parts (manufactured by Lion Akzo) Toluene 1500 parts Tested in the same manner as in Example 53 using this carrier and toner. Similar results to Example 53 were obtained.

[Example 64] The toner used in Example 53 was used. On the other hand, for the carrier, the coating liquid was prepared according to the following formulation. Then, the same core material as in Example 53 was coated. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Conductive agent: Ketjen Black ECDJ600 4 parts (Lion Akzo) Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Toluene 1500 parts This carrier and toner When used in the same manner as in Example 53, the same results as in Example 53 were obtained.

[Example 65] The toner used in Example 53 was used. On the other hand, the carrier was prepared by adjusting the coating liquid according to the following formulation and coating the core material. A synthetic example of a hydroxyl group-containing acrylic resin was prepared by charging 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer and heating to 100 ° C., 400 g of styrene, 160 g of methyl methacrylate, and 200 g of n-butyl acrylate.
g, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator were added dropwise over 5 hours.
Then, the contents were reacted for another 6 hours to obtain a resin having a solid content of 50%. (Hydroxyl value: 41 KOHmg / g, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) Fully substituted methylated benzoguanamine 2.6 parts (polymerization degree 1. 65, solid content 77%) Acrylic resin (the above synthetic product: solid content 50%) 10 parts Toluene 300 parts

A coating was prepared by mixing the above methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and the toner were used and tested in the same manner as in Example 53, the same results as in Example 53 were obtained.

[Example 66] The toner used in Example 53 was used. On the other hand, the carrier was prepared by adjusting the coating liquid according to the following formulation and coating the core material. A synthetic example of a hydroxyl group-containing acrylic resin was prepared by charging 700 g of xylene and 300 g of butanol in a nitrogen stream while stirring with a stirrer and heating to 100 ° C., 400 g of styrene, 160 g of methyl methacrylate, and 200 g of n-butyl acrylate.
g, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator were added dropwise over 5 hours. Then, the contents were reacted for another 6 hours to obtain a solid content of 50.
% Resin was obtained. (Hydroxyl value: 41 KOHmg / g, number average molecular weight 1400) Cu-Zn ferrite 1000 parts (manufactured by Powdertec Co., average particle size 50 μm, F-300) Fully substituted methylated benzoguanamine 2.6 parts (polymerization degree 1. 65, solid content 77%) Acrylic resin (synthetic product: solid content 50%) 10 parts Conductive agent: Ketjen Black ECDJ600 2.5 parts (manufactured by Lion Akzo) Toluene 300 parts

A coating was prepared by mixing the above methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed type coating apparatus containing the above ferrite was kept at about 60 ° C. and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled and crushed to obtain a resin-coated carrier having a film thickness of 0.2 μm. When this carrier and the toner were used and tested in the same manner as in Example 53, the same results as in Example 53 were obtained.

[Example 67] As a carrier, a coating solution was prepared according to the following formulation. Silicone resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle diameter of 50 μ, which is composed of a core material surface having irregularities. 230 ° C after coating
Then, the silicon film was cured under heating for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), surface irregularities could be observed even after clear coating. Further, it was confirmed by an electron beam microanalyzer that Si element was present also in the convex portion.

On the other hand, as the toner, a yellow toner was prepared as follows. Binder resin: 100 parts of the production example of polyester resin 1 Yellow colorant: C.I. I. Pigment Yellow 180 5 parts Charge control agent: from Production Example 4 2 parts

This is premixed with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled and roughly crushed to 0.5 to 3 mm, and then further crushed and classified to have an average particle size of 7.75μ, and a number% of 5μ or less is 12.8.
A yellow toner having a volume% of 5, 16 μ or more and 0.07 was obtained.

0.0 to 100 parts by weight of the toner
16 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.5 part to obtain a negatively chargeable toner. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = -18 B: Q / M of toner particles after addition of external additive = -23 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0026

A magenta toner was prepared by the following toner prescription. Binder resin: manufactured from Polyester resin 1 100 parts Magenta Colorant: C.I. I. Pigment Red 122 4 parts Charge control agent: of Production Example 4 2 parts

This is premixed with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled and roughly crushed to 0.5 to 3 mm, and then further crushed and classified to have an average particle size of 7.75μ, and a number% of 5μ or less is 12.8.
Magenta toner having a volume% of 5, 16 μ or more and 0.07 was obtained.

0.0 to 100 parts by weight of the toner
Silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) having a particle size of 16 μm was mixed at a ratio of 0.5 part to obtain a toner having a negative charging property. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = −14 B: Q / M of toner particles after addition of external additive = −19 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0028

Cyan toner was prepared by the following toner prescription. Binder resin: manufactured from Polyester resin 1 100 parts Cyan colorant: C.I. I. Pigment Blue 15: 3 3 parts Charge control agent: of Production Example 4 2 parts

Preliminary kneading of this product is carried out with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled and roughly crushed to 0.5 to 3 mm, and then further crushed and classified to have an average particle size of 7.75μ, and a number% of 5μ or less is 12.8.
A cyan toner having a volume% of 5,16 μm or more and 0.07 was obtained.

0.0 to 100 parts by weight of the toner
16 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed at a ratio of 0.5 part to obtain a negatively chargeable toner. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = -18 B: Q / M of toner particles after addition of external additive = -22 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0025

A black toner was prepared by the following toner formulation. Binder resin: Polyester resin 1 manufactured example 100 parts Black colorant: carbon black 8 parts Charge control agent: manufactured example 4 2 parts This is premixed with a mixer. After that, the mixture is melt-kneaded with a three-roll mill, cooled, roughly crushed to 0.5 to 3 mm, and further crushed and classified to obtain an average particle size of 7.7.
A black toner having a number% of 5 μ or less and 5 μ or less of 12.85 and a volume percentage of 16 μ or more of 0.07 was obtained.

0.0 based on 100 parts by weight of the toner.
Silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) having a particle size of 16 μm was mixed at a ratio of 0.5 part to obtain a toner having a negative charging property. On the other hand, the carrier described above is used, the toner is composed of only toner base particles, and the toner base particles are toner particles after addition of an external additive, and the charge amount of each developer is measured. The result is as follows. A: Q / M of toner base particles = −13 B: Q / M of toner particles after addition of external additive = −18 C: Silica having an average particle size of 0.016 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.0029

The above carrier is used, and the total amount of 5 parts of the toner of each color and the carrier is 100.
By mixing in a ratio of parts, yellow, magenta, cyan, and black developers were prepared. The developers of the respective colors were obtained by modifying the pre-tail 750 (a color copying machine manufactured by Ricoh) so that the recycled toner could be returned to the toner replenishing section. When a developer is set and an image is output, toner transferability is good, there is no toner dust in the image area, there is no toner loss in the character area, moderate image gloss is maintained, and there is no background stain, and a good image is obtained. Was given. Also, 10 ° C / 15%, 30 ° C / 90
%, Good images were obtained even after images were printed in each environment and after copying 10,000 sheets in each environment.

[Example 68] In Example 67, only the resin of each color toner was changed as follows. <Production Example of Polyester Resin 2> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2
-Bis (4-hydroxyphenyl) propane, terephthalic acid and 1,2,4-benzenetricarboxylic acid were added and condensation was carried out by an ordinary method to give an acid value of 35 (KOHmg /
The resin of g) was obtained. Binder resin: Polyester resin 2 production example 100 parts Toner was prepared in the same manner as in Example 67, and Example 67 was used.
When the same additive as in Example 67 was used and the same carrier as in Example 67 was used and the same test as in Example 67 was carried out, the same result as in Example 67 was obtained.

Example 69 <Production Example of Polyester Resin 3> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and terephthalic acid were added and condensation was carried out by a conventional method. A resin having an acid value of 2.2 (KOHmg / g) was obtained. Binder resin: Polyester resin 3 production example 100 parts Toner was prepared in the same manner as in Example 67, and Example 67 was used.
When the same additive as in Example 67 was used and the same carrier as in Example 67 was used and the same test as in Example 67 was carried out, the same result as in Example 67 was obtained.

[Example 70] In Example 67, only the resin of each color toner was changed as follows. <Production Example of Polyester Resin 4> Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, terephthalic acid, succinic acid, trimellitic acid / is condensed by an ordinary method to give an acid value of 42. (KOHmg
/ G) of resin was obtained. Binder resin: Production example of polyester resin 4 100 parts Toner was prepared in the same manner as in Example 67, and Example 67 was used.
When the same additive as in Example 67 was used and the same carrier as in Example 67 was used and the same test as in Example 67 was carried out, the same result as in Example 67 was obtained.

[Embodiment 71] Embodiment 6 is different from Embodiment 67 except that the carrier of Embodiment 66 is changed.
When tested in the same manner as in Example 7, the same result as in Example 67 was obtained.

[Example 72] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have a mean particle size of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Polyester resin 1 production example 100 parts Polypropylene 5 parts Colorant: Carbon black 11 parts Charge control agent: Production example 1-2 1.5 parts Average particle based on 100 parts by weight of the toner Diameter 0.015
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene and a resin having a weight ratio of 75/25 and a ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles after addition of external additives. The toner is charged with each toner, and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base The particle X is 0.0024.

Only that toner is put into the apparatus shown in FIG. The operation of the device is as follows. The toner (6) stored in the toner tank (7) is a stirring blade (5).
Is forced to the sponge roller (4), and the toner (6) is supplied to the sponge roller (4). Then, the toner (6) taken into the sponge roller (4) is conveyed to the toner conveying member (2) and rubbed by the rotation of the sponge roller (4) in the direction of the arrow, and electrostatically or physically. The toner transport member (2) strongly rotates in the direction of the arrow, and the elastic blade (3) forms a uniform thin toner layer and is triboelectrically charged. After that, the latent image is carried to the surface of the latent image carrier (1) which is in contact with or close to the toner transport member (2), and the latent image is developed. The electrostatic latent image is image-exposed after the latent image carrier (1) is DC-charged at -300 V to form a latent image, and then the latent image is developed. Then, the toner image is fixed on a transfer member (not shown) by a fixing device after transfer. Further, the latent image carrier (1) is cleaned of transfer residual toner by a cleaning section (not shown), and the cleaned toner is returned to the toner tank (7) to prepare for the next electrostatic latent image formation.

In this way, when the developer was set and an image was produced, the toner transferability was good, there was no toner dust in the image area, there was no toner loss in the character area, and a suitable image gloss was maintained. A good image was obtained without stains. Also, good images were obtained even after images were printed in each environment of 10 ° C./15% and 30 ° C./90%, and after copying 10,000 sheets in each environment. When the initial image was printed, a good image was obtained.

[Example 73] Using only the toner of Example 72, the IPSiO NX1100 (copier manufactured by Ricoh Co., Ltd.) was modified so that the recycled toner returned to the toner developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, 10000
When a continuous paper feed test of 0 sheets was carried out, a good image was not found, and toner scattering was not observed in the copying machine. Also, when the copying process was stopped midway and the latent image bearing member was observed, it was stained with toner. Was not seen, and it was confirmed that there was no problem. Then 10 ℃ / 15%, 30 ℃ / 90%
In each of the above environments, a test of continuous sheet passing of 10,000 sheets was conducted, but no particular problem occurred.

[Example 74] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle diameter of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Polyester resin 1 production example 100 parts Polypropylene 5 parts Magnetic material 50 parts Colorant: Carbon black 11 parts Charge control agent: Preparation example 4 1.5 parts To 100 parts by weight of the toner, Average particle size 0.015
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm.

On the other hand, as the carrier, a copolymer of 2-hydroxyethyl metallate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene was used in a resin having a weight ratio of 75/25 and ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles after addition of external additives.
The charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base Particle X = 0.024

Now, using only the above toner, the IPS
The iO NX610 (Ricoh copier) was modified so that recycled toner returned to the developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found and toner scattering was not found in the copying machine. Further, when the copying process was stopped halfway and the latent image bearing member was observed, the toner was found to be toner. It was confirmed that there was no problem, and no problem was found. Then 1
1 for each environment of 0 ° C / 15% and 30 ° C / 90%
A continuous paper feed test of 0000 sheets was conducted, but no particular problem occurred.

[Example 75] An IPSiO Color 5000 (Ricoh copying machine) was modified by using only the toner of Example 67 so that the recycled toner could return to the developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, 10000
When a continuous paper feed test of 0 sheets was carried out, a good image was not found, and toner scattering was not observed in the copying machine. Also, when the copying process was stopped midway and the latent image bearing member was observed, it was stained with toner. Was not seen, and it was confirmed that there was no problem. Then 10 ℃ / 15%, 30 ℃ / 90%
In each of the above environments, a test of continuous sheet passing of 10,000 sheets was conducted, but no particular problem occurred.

[Example 76] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle size of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Polypropylene: 5 parts Colorant: carbon black 11 parts Charge control agent: of Production Example 4 1.5 parts To 100 parts by weight of the toner, Average particle size 0.015
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm.

On the other hand, as a carrier, a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene was used at a weight ratio of 75/25 and a resin having an average particle diameter of 50 μm ferrite. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles after addition of external additives.
The charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base The particle X is 0.0024.

Only the toner is put into the apparatus shown in FIG. In this way, when the developer was set and the initial image was output, the toner transferability was good, there was no toner dust in the image area, there was no toner loss in the text area, and a suitable image gloss was maintained and background smearing occurred. Nonetheless, a good image was obtained. Also, good images were obtained even after images were printed in each environment of 10 ° C./15% and 30 ° C./90%, and after copying 10,000 sheets in each environment.

[Embodiment 77] Using only the toner of Embodiment 1, the IPSiONX1100 (copier manufactured by Ricoh Co., Ltd.) was remodeled so that the recycled toner would return to the developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found and toner scattering was not seen in the copying machine. Further, when the copying process was stopped midway and the latent image bearing member was observed, It was confirmed that there was no problem due to no stain due to. After that, a test of 10,000 sheets of continuous paper passing was carried out in each environment of 10 ° C./15% and 30 ° C./90%, but no particular problem occurred.

[Example 78] A toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to have an average particle diameter of 7.75 µm and a number% of 5 µ or less. Was 12.85, and a toner base particle having a volume percentage of 16 μ or more and 0.07 was obtained. Binder resin: Resin of resin 1 70 parts: Resin of resin 15 30 parts Polypropylene: 5 parts Magnetic material: 50 parts Colorant: Carbon black 11 parts Charge control agent: of Production Example 1.5 1.5 parts The toner 100 weight Average particle size 0.015
Negatively chargeable developing toner was prepared by mixing 0.3 μm of silica having a particle size of 0.3 μm.

On the other hand, the carrier is a copolymer of 2-hydroxyethyl metal relate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene and a resin having a weight ratio of 75/25 and a ferrite having an average particle size of 50 μm. 0.75% by weight of core material (core material standard)
Was coated to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g is weighed), the toner and the carrier are charged in a pot, and the mixture is mixed at 150 rpm for 10 minutes. Measure (Q / M). At this time, the toner is composed of toner base particles and toner particles to which external additives have been added. Each toner is charged and the charge amount (Q / M) of each developer is measured. The result is as follows. A: Q / M of toner base particles = −17 B: Q / M of toner particles after addition of external additive = −21 C: Silica having an average particle size of 0.015 μm D: Average particle size of 7.75 μm Toner base The particle X is 0.0024.

Here, using only the above toner, the IPS
The iO NX610 (Ricoh copier) was modified so that the recycled toner returned to the developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, when a continuous paper feed test of 100,000 sheets was carried out, no good image was found and toner scattering was not seen in the copying machine. Further, when the copying process was stopped midway and the latent image bearing member was observed, It was confirmed that there was no problem due to no stain due to. Then 10
10 in each environment of ℃ / 15%, 30 ℃ / 90%
A test for continuously passing 000 sheets was conducted, but no particular problem occurred.

[Example 79] Using only the toner of Example 32, the IPSiO Color 5000 (a copying machine manufactured by Ricoh Co., Ltd.) was modified so that the recycled toner was returned to the developing section. When the toner was set and the initial image was formed, a good image was obtained. Furthermore, 10000
When a continuous paper feed test of 0 sheets was carried out, a good image was not found, and toner scattering was not observed in the copying machine. Also, when the copying process was stopped midway and the latent image bearing member was observed, it was stained with toner. Was not seen, and it was confirmed that there was no problem. Then 10 ℃ / 15%, 30 ℃ / 90%
In each of the above environments, a test of continuous sheet passing of 10,000 sheets was conducted, but no particular problem occurred.

[Example 80] A black toner was prepared in the same manner as in Example 32 except that 25 parts of a magnetic material was added to the black toner formulation only. When tested in the same manner as in Example 32, the same results as in Example 32 were obtained.

[Example 81] In Example 32, only the colorants of yellow, magenta, and cyan were replaced with those shown in Table 2 in the toner formulation (black is Example 8).
No. 0 was used) to prepare a toner in the same manner as in Example 32. When tested in the same manner as in Example 32, the same results as in Example 32 were obtained.

[0227]

[Table 2]

[0228]

As is clear from the detailed and specific description above, according to the present invention, even if the developer before opening is used after long-term storage, the decrease in the charge amount is extremely small, and the charge amount is decreased. Even if the copying machine is used (opened), the amount of charge quickly increases, and even after the copier is left unused for a long period of time, the amount of charge quickly rises during use and no toner scatters. Provided is a two-component developer which does not cause scumming on the area.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a developing device used in the present invention.

[Explanation of symbols]

1 Latent image carrier 2 Toner transport member 3 elastic blade 4 Sponge roller 5 stirring blades 6 toner 7 Toner tank

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/113 G03G 9/08 333 15/01 114 361 15/08 504 9/10 351 507 9/08 101 21/10 15/08 507D 21/00 312 (72) Inventor Kazuhiko Umemura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Hideki Sugiura 1-3-3 Nakamagome, Ota-ku, Tokyo No. 6 In Ricoh Company (72) Inventor Minoru Masuda 1-3-6 Nakamagome, Ota-ku, Tokyo In-house Ricoh Company (72) Tomomi Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Within Ricoh Company (72) Inventor Kosuke Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo F-terms within Ricoh Company (Reference) 2H005 AA01 AA02 AA08 BA06 CA07 CA08 CA16 CA2 5 DA02 EA01 EA05 EA06 EA07 FA02 2H030 AD01 AD03 BB22 BB43 BB53 BB71 2H077 AA37 AC16 AD02 AD06 AD13 AD17 EA01 GA13 2H134 GA01 GB02 JA01 JA11 JB01 KA15 KA20 KA24 K01 K12 KG04 H01 K08 K01 K02 K08 K02 K08 K02 K08 K01 K02 K08 K02 K08 K02 K01

Claims (13)

[Claims] 1. A developer carrying member layer is formed, and a developing unit for developing an electrostatic latent image on an electrostatic latent image carrying member contains a two-component developer consisting of a carrier and a toner. , The developer is circulated and conveyed on the developer carrier, and an electrostatic latent image is developed in a developing region in a gap between the developer and the electrostatic latent image carrier facing the developer, and is formed on the electrostatic latent image carrier. The formed toner image is transferred onto the transfer member once or a plurality of times, the electrostatic latent image carrier is cleaned by a cleaning unit, and the toner cleaned by the cleaning unit is transferred to a developing unit or a toner collecting device. It is returned to the supply toner section,
After that, the latent image carrier prepares for the next electrostatic latent image, and the toner image is transferred to the final transfer member and then fixed by the fixing unit.
The toner particles are composed of base particles including at least a colorant, a binder resin, and a charge control agent, to which an external additive is added,
The charge control agent is composed of a salicylic acid metal complex compound, the conductivity thereof is 950 μS / cm or less, the charge amount of the toner base particles is A, and the toner charge after adding at least one or more external additives to the toner base particles. When the amount is B, the average particle size of the external additive is C, and the average particle size of the toner base particles is D, respective values are given by the following formula: X = (B / A) × (ΣC / D) The value of X obtained by substituting
X ≦ 2.3, the binder resin is an epoxy resin, an alkylene oxide adduct of a dihydric phenol or its glycidyl ether, a dihydric phenol,
A polyol (A) obtained by reacting an active hydrogen that reacts with an epoxy group with a compound having one in the molecule, an epoxy resin, a dihydric phenol, and a compound having one active hydrogen in the molecule that reacts with an epoxy group. A two-component developer comprising a polyol (B) formed by reacting with. 2. The binder resin of the toner is at least two kinds of bisphenol A type epoxy resins in which the epoxy resins constituting the polyol (A) have different number average molecular weights, and the low molecular weight component has a number average molecular weight of 360. ~ 200
0, the number average molecular weight of the high molecular weight component is 3000 to 1
The two-component developer according to claim 1, wherein the two-component developer is 0000. 3. The toner binder resin, wherein the epoxy resin constituting the polyol (A) is at least two bisphenol A type epoxy resins having different number average molecular weights, and the low molecular weight component is 20 to 60 wt%. The two-component developer according to claim 1, wherein the high molecular weight component is 5 to 40 wt%. 4. The binder resin for the toner is a diglycidyl ether of an alkylene oxide adduct of a dihydric phenol or a glycidyl ether of a dihydric phenol constituting a polyol (A), and the following general formula: The two-component developer according to claim 1, which is represented by the formula (1). [Chemical 1] n and m are the number of repeating units, each is 1 or more, and n + m = 2 to 8. ) 5. The toner binder resin is characterized by containing 10 to 50 wt% of an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof constituting a polyol (A) with respect to an epoxy resin. The two-component developer according to claim 1. 6. The two-component developer according to claim 1, wherein the toner binder resin has a number average molecular weight of polyol (B) of 200 to 10,000. 7. The two-component developer according to claim 1, wherein the toner binder resin contains 20 to 50 wt% of polyol (B). 8. The two-component developer according to claim 1, wherein the toner binder resin is a polyester resin. 9. The two-component developer according to claim 1, wherein the colorant of the toner comprises yellow, magenta, cyan and black which are different from each other. 10. The two-component developer according to claim 1, wherein the surface of the carrier particles is coated with a resin. 11. A developer carrying layer is formed, and a developing section for developing an electrostatic latent image on an electrostatic latent image carrying body contains a two-component developer consisting of a carrier and a toner. ,
The developer is circulated and conveyed on the developer carrier, and an electrostatic latent image is developed in a developing area in a gap between the developer and the electrostatic latent image carrier facing the developer, and the developer is formed on the electrostatic latent image carrier. The toner image is transferred onto the transfer member one or more times, the electrostatic latent image carrier is cleaned by the cleaning unit, and the toner cleaned by the cleaning unit is supplied to the developing unit or the replenishing unit via the toner collecting device. After being returned to the toner section, the latent image carrier prepares for formation of the next electrostatic latent image,
An image forming method in which a toner image is transferred to a final transfer member and then fixed by a fixing unit, wherein the toner particles include at least a colorant, a binder resin, and a charge control agent as an external additive to base particles. Is added, the charge control agent is composed of a salicylic acid metal complex compound, and its conductivity is 950.
The toner charge amount of the toner base particles is A, the toner charge amount after adding at least one or more external additives to the toner base particles is B, the average particle diameter of the external additive is C, and the toner base is When the average particle diameter of the particles is D, the value of X obtained by substituting the respective values into the following equation: X = (B / A) × (ΣC / D) is −2.3 ≦
An image forming method characterized in that X ≦ 2.3. 12. A method for developing an electrostatic latent image using the two-component developer according to claim 1, wherein a toner layer regulating member on the toner conveying member is used. Then, after forming a thin toner layer, toner is supplied onto the latent image carrier to develop the image. 13. The image forming method according to claim 12, wherein the toner is a magnetic toner containing a magnetic material.